CN111684005B

CN111684005B - Cellulose esters and polymerized aliphatic polyester compositions and articles

Info

Publication number: CN111684005B
Application number: CN201980013272.6A
Authority: CN
Inventors: 安海宁; 冯文来; M·E·唐纳森; T·J·佩科里尼
Original assignee: Eastman Chemical Co
Current assignee: Eastman Chemical Co
Priority date: 2018-02-13
Filing date: 2019-02-13
Publication date: 2022-10-28
Anticipated expiration: 2039-02-13
Also published as: JP2021512985A; JP2023179492A; US20200399445A1; EP3752557A1; CN111684004A; JP7408555B2; US11555100B2; CN111684004B; JP2021512988A; CN111684005A; EP3752558A1; WO2019160908A1; JP7408554B2; WO2019160906A1; JP2023179493A; US20200399446A1; US11873390B2

Abstract

A cellulose ester composition is provided comprising at least one cellulose ester, at least one polymeric aliphatic polyester, at least one impact modifier, and at least one monomeric plasticizer. Also provided are methods of producing the cellulose ester compositions and articles, such as eyewear or sunglass frames and/or lenses, made using these compositions.

Description

Cellulose esters and polymerized aliphatic polyester compositions and articles

Technical Field

The present invention is in the field of cellulose ester chemistry, particularly cellulose esters comprising Polymeric Aliphatic Polyesters (PAP), impact modifiers, and monomeric plasticizers. Also provided are methods of producing these cellulose ester compositions and plastic articles, such as eyeglass frames, automotive parts, and toys, made using these compositions.

Background

The cellulose ester compositions typically have a Heat Distortion Temperature (HDT) or glass transition temperature (Tg) of less than 90 ℃. Commercially available cellulose esters that are melt processed into articles typically contain significant amounts of monomeric plasticizers to allow processing and impart sufficient toughness to the molded articles. However, the addition of large amounts of monomeric plasticizers has disadvantages in that they will reduce the HDT relative to the base cellulose ester and limit the use of cellulose ester materials to applications that can accommodate HDT below about 90 ℃. Common monomeric plasticizers for cellulose ester molded articles also experience plasticizer bleed during processing and use.

It would be beneficial to be able to provide melt processable cellulose ester compositions that do not suffer from these disadvantages.

Summary of The Invention

It has been surprisingly found that cellulose ester compositions comprising Cellulose Acetate Propionate (CAP) can be prepared having a glass transition temperature (Tg's) of about 110 ℃ or 120 ℃ or greater and having good clarity and toughness. In embodiments of the invention, this may be achieved by reducing the amount of monomeric plasticizer in the composition. Reducing the monomer plasticizer may limit or eliminate the common problems associated with monomer plasticizer bleed-out during use. However, reducing the monomeric plasticizer reduces the toughness of these high Tg cellulosic compositions. It has been surprisingly found that certain combinations of polymers of the CAP and polybutylene succinate family, which may include other polymeric aliphatic polyesters (e.g., succinates, glutarates, or adipates of polyethylene glycol, polypropylene glycol, or polybutylene glycol) and may include different co-or ter-monomers (collectively referred to as PBS polymers or PAP, as defined below), can restore toughness to high Tg cellulosic compositions and provide cellulose ester compositions with good flow properties and good clarity suitable for higher temperature applications and maintaining long-term dimensional stability.

In certain embodiments, the present invention relates to one or more PAPs, such as poly (butylene succinate) ("PBS"), dispersed into a cellulose ester composition in an amount sufficient to improve the mechanical and physical properties of the cellulose ester composition. PAP (e.g., PBS) modified cellulose esters according to embodiments of the present invention have unique properties of being melt processable, having Tg's significantly higher than commercially available plasticized cellulose ester thermoplastics, high modulus, good impact properties, and good load deflection resistance. In embodiments, the PBS polymer (or PAP) modified cellulose ester can have good gate strength and/or acoustic damping properties.

In one embodiment of the invention, a cellulose ester composition is provided comprising at least one cellulose ester and at least one PAP (e.g., PBS). In one embodiment, the cellulose ester is selected from cellulose acetate propionate containing from about 10 to about 40 weight percent propionyl, based on the total weight of the polymer, and the cellulose ester composition has a Tg of at least 120 ℃. In certain embodiments, the cellulose ester composition has a Tg of at least 140 ℃ or at least 150 ℃.

In another embodiment of the invention, a cellulose ester composition is provided comprising at least one cellulose ester and at least one PAP and at least one impact modifier. In another embodiment of the invention, a cellulose ester composition is provided comprising at least one cellulose ester and at least one PAP, at least one impact modifier, and 1 wt% to less than 5 wt% of a monomeric plasticizer.

In another embodiment of the present invention, a process for producing a cellulose ester composition is provided, the process comprising contacting at least one cellulose ester, at least one PAP, at least one impact modifier, and at least one monomeric plasticizer, and mixing the combination. In one embodiment, the cellulose ester composition comprises a monomeric plasticizer present in an amount that does not significantly reduce the Tg of the cellulose ester composition as compared to a similar composition without the monomeric plasticizer. In embodiments, the Tg changes (e.g., decreases) by no more than 10%, or 5%, or 2% due to the inclusion of the monomeric plasticizer.

In an embodiment of the invention, a cellulose ester composition is described that contains less than 5 wt% of a monomeric plasticizer, based on the total weight of the cellulose ester composition, but contains from 1 wt% to 35 wt%, or from 2.5 wt% to 30 wt%, or from 5 wt% to 20 wt%, or from 6 wt% to 18 wt%, or from 7 wt% to 15 wt% of PAP, and has a Tg value of greater than 120 ℃, or at least 140 ℃, or at least 150 ℃, and has a notched izod impact value of greater than 80, or 100, or 110, or 125, or 150, or 175, or 200J/m at 23 ℃.

In another embodiment of the present invention, a cellulose ester composition is provided that contains less than 5 wt% monomeric plasticizer, but is melt processable. In embodiments, the melt processable cellulose ester composition contains from 1 to 35 wt.%, or from 2.5 to 30 wt.%, or from 5 to 20 wt.%, or from 6 to 18 wt.%, or from 7 to 15 wt.% PAP, based on the total weight of the cellulose ester composition, and has a Tg value of greater than 120 ℃, or at least 140 ℃, or at least 150 ℃, a notched izod impact value of greater than 80, or 100, or 110, or 125, or 150, or 175, or 200J/m at 23 ℃, and a spiral flow value of at least 38 centimeters (15 inches) when measured at a barrel temperature of 240 ℃ using the procedures described herein.

In embodiments, the monomeric plasticizer is present in an amount that does not significantly reduce the Tg of the cellulose ester composition as compared to a similar composition without the monomeric plasticizer. In embodiments, the Tg changes (e.g., decreases) by no more than 10%, or 5%, or 2% due to the inclusion of the monomeric plasticizer.

In one embodiment of the invention, a polymer-based resin is provided comprising at least one cellulose ester, at least one PAP, and at least one monomeric plasticizer, wherein the cellulose ester is CAP and the PAP is PBS, and wherein the resin contains 0 wt% to 5 wt%, 0 to less than 5 wt%, 0 wt% to 4 wt%, 0 wt% to 2 wt%, or 0 wt% to 1 wt% monomeric plasticizer. In one embodiment, the cellulose ester is CAP and the resin contains less than 5 wt% monomeric plasticizer. In one embodiment, the cellulose ester is CAP, PBS has an MFR (190 ℃,2.16 kg) of less than 10 and an elongation at break of 200% or more, and the resin contains less than 5 wt% monomeric plasticizer and less than 10 wt% or less than 8 wt% of any other additives. However, in some embodiments, the resin may also include additional pigments or colorants or optical additives for opacifying/tinting applications, such as titanium dioxide.

In certain embodiments, the PAR has an MFR of less than 30 measured at 190 ℃ with a 2.16 kg load according to ASTM test method D1238.

In certain embodiments, the cellulose ester resin is selected from at least one Cellulose Propionate (CP), cellulose Butyrate (CB), cellulose Acetate Propionate (CAP), cellulose Acetate Butyrate (CAB), cellulose Acetate Isobutyrate (CAIB), cellulose Propionate Butyrate (CPB), cellulose Tripropionate (CTP), or Cellulose Tributyrate (CTB). In certain embodiments, the resin contains less than 25, or less than 20, or less than 15, or less than 10, or less than 5 weight percent, or is completely free of any other polymer or polymers that contribute to the continuous binder phase of the resin and cellulose ester. For example, in certain embodiments, PAP (e.g., PBS) is present as a dispersed phase within the cellulose ester resin and does not contribute to the continuous binder phase of the resin and cellulose ester.

In certain embodiments, the cellulose ester resin is selected from at least one Cellulose Propionate (CP), cellulose Butyrate (CB), cellulose Acetate Propionate (CAP), cellulose Acetate Butyrate (CAB), cellulose Acetate Isobutyrate (CAIB), cellulose Propionate Butyrate (CPB), cellulose Tripropionate (CTP), or Cellulose Tributyrate (CTB), and the PAP (e.g., PBS) is miscible in the cellulose ester resin, or in the same phase as the cellulose ester binder. In certain embodiments, the cellulose ester resin and PAP (e.g., PBS) are miscible, and the cellulose ester composition further comprises an impact modifier. In one embodiment, the impact modifier is a core shell impact modifier. In one embodiment, the impact modifier is an acrylic core-shell impact modifier.

In certain embodiments, a cellulose ester composition is provided comprising at least one cellulose ester, at least one PAP, at least one impact modifier, and 1 to less than 5 wt% monomeric plasticizer. In embodiments, the PAP, impact modifier, and monomeric plasticizer are present in amounts sufficient to provide a composition that is capable of being molded and has a balance of relatively high Tg, good toughness, creep (i.e., load deflection) resistance, and good gate strength. In embodiments, the cellulose ester is CAP, PAP is PBS, the impact modifier is an acrylic core-shell impact modifier, and the monomeric plasticizer is an adipate-based monomeric plasticizer (e.g., DOA), and the composition comprises 2 to 10, or 3 to 8, weight percent PBS;2 to 10 wt%, or 4 to 8 wt% of an impact modifier; and 2 to less than 5 wt% of a monomeric plasticizer. In one embodiment, the monomeric plasticizer is DOA.

In certain embodiments, for any of the embodiments above, the one or more PAPs comprise PBS or a copolymer of poly (butylene succinate) and poly (butylene adipate) (PBSA). In certain embodiments, for any of the embodiments above, the PAP is PBS or PBSA. In certain embodiments, for any of the embodiments above, the PAP is PBS.

In certain embodiments, the cellulose ester may be selected from cellulose acetate butyrate containing from about 5 to about 55 weight percent butyryl groups, based on the total weight of the polymer. In certain embodiments, the cellulose ester may be selected from cellulose acetate propionate containing from about 5 to about 50 weight percent propionyl, based on the total weight of the polymer.

In certain embodiments, the cellulose ester is a Cellulose Acetate Propionate (CAP) having a propionyl content of greater than 5 wt% based on the total weight of the polymer. In certain embodiments, the cellulose ester is a Cellulose Acetate Propionate (CAP) having a propionyl content greater than 40% based on the total weight of the CAP polymer. In certain embodiments, the cellulose ester is a Cellulose Acetate Propionate (CAP) having a propionyl content of less than 40% based on the total weight of the CAP polymer.

In certain embodiments, the cellulose ester is a Cellulose Acetate Butyrate (CAB) having a butyryl content greater than 5 weight percent, based on the total weight of the polymer. In certain embodiments, the cellulose ester is a Cellulose Acetate Butyrate (CAB) having a butyryl content greater than 40% based on the total weight of the CAB polymer. In certain embodiments, the cellulose ester is a Cellulose Acetate Butyrate (CAB) having less than 32% butyryl content or 15 to 32% by weight butyryl content, based on the total weight of the CAB polymer.

Brief Description of Drawings

Embodiments of the present disclosure are described herein with reference to the following drawings, wherein:

FIG. 1 is a schematic view of a picture frame mold used to mold square picture frame trial articles for gate strength testing.

Detailed description of the invention

In one embodiment of the invention, a cellulose ester composition is provided comprising at least one cellulose ester, at least one PAP, at least one impact modifier, and at least one monomeric plasticizer.

In embodiments, the cellulose ester used in the present invention may be of C ₃ To C ₁₀ Any cellulose ester in sufficient amounts of the salt or ester portion of the acid, preferably the propionate and/or butyrate portion. The cellulose esters useful in the present invention generally comprise repeating units having the structure:

wherein R is ¹ 、R ² And R ³ Independently selected from hydrogen or straight alkanoyl having 2 to 10 carbon atoms. For cellulose esters, the substitution level is typically expressed in terms of Degree of Substitution (DS), which is the average number of non-OH substituents per anhydroglucose unit (AGU). Typically, conventional cellulose contains three hydroxyl groups in each AGU unit that may be substituted; thus, DS may have a value of 0 to 3. However, low molecular weight cellulose mixed esters may have an overall degree of substitution slightly above 3 due to end group contribution. Natural cellulose is a large polysaccharide having a degree of polymerization of 250 to 5,000 even after pulping and purification, andand the assumption that the maximum DS is 3.0 is therefore approximately correct. However, as the degree of polymerization decreases, as in low molecular weight cellulose mixed esters, the end groups of the polysaccharide backbone become relatively more pronounced, thereby resulting in a possible DS variation of over 3.0. Low molecular weight cellulose mixed esters are discussed in more detail later in this disclosure. Since DS is a statistical average, a value of 1 does not ensure that each AGU has a single substituent. In some cases, there may be unsubstituted anhydroglucose units, some with two substituents and some with three substituents, and this value is typically not an integer. The total DS is defined as the average of all substituents per anhydroglucose unit. The degree of substitution/AGU may also refer to a specific substituent, such as hydroxy, acetyl, butyryl or propionyl.

In embodiments, the cellulose ester used may be a cellulose triester or a type II (secondary) cellulose ester. Examples of cellulose triesters include, but are not limited to, cellulose tripropionate or cellulose tributyrate. Examples of the cellulose ester of type II include cellulose acetate propionate and cellulose acetate butyrate.

In one embodiment of the present invention, the cellulose ester may be selected from Cellulose Propionate (CP), cellulose Butyrate (CB), cellulose Acetate Propionate (CAP), cellulose Acetate Butyrate (CAB), cellulose Propionate Butyrate (CPB), cellulose Acetate Isobutyrate (CAIB), cellulose Tripropionate (CTP), cellulose Tributyrate (CTB), or the like, or a combination thereof. Some examples of cellulose esters are described in U.S. Pat. nos. 1,698,049;1,683,347;1,880,808;1,880,560;1,984,147, 2,129,052; and 3,617,201, which are incorporated herein by reference in their entirety to the extent not inconsistent with the statements herein. In one embodiment, the cellulose ester is CAP.

In one embodiment of the present invention, the cellulose ester may be selected from Cellulose Propionate (CP), cellulose Butyrate (CB), cellulose Acetate Propionate (CAP), cellulose Acetate Butyrate (CAB), cellulose Acetate Isobutyrate (CAIB), cellulose Propionate Butyrate (CPB), cellulose Tripropionate (CTP), or Cellulose Tributyrate (CTB), but not from Cellulose Acetate (CA).

In some embodiments of the present invention, the substrate is, the cellulose ester has from 5 to 52%, or from 10 to 52%, or from 15 to 52%, or from 20 to 52%, or from 25 to 52%, or from 30 to 52%, or from 35 to 52%, or from 40 to 52%, or from 45 to 52%, or from 49 to 52%, or from 5 to 50%, or from 10 to 50%, or from 15 to 50%, or from 20 to 50%, or from 25 to 50%, or from 30 to 50%, or from 35 to 50%, or from 40 to 50%, or from 45 to 50%, or from 5 to less than 50%, or from 10 to less than 50%, or from 15 to less than 50%, or from 20 to less than 50%, or from 25 to less than 50%, or from 30 to less than 50%, based on the total weight of the cellulose ester polymer or 35 to less than 50%, or 40 to less than 50%, or 45 to less than 50%, or 5 to 38%, or 10 to 38%, or 15 to 38%, or 20 to 38%, or 25 to 38%, or 30 to 38%, or 35 to 38%, or 5 to 35%, or 10 to 35%, or 15 to 35%, or 20 to 35%, or 25 to 35%, or 30 to 35%, or 5 to 30%, or 10 to 30%, or 15 to 30%, or 20 to 30%, or 25 to 30%, or 5 to 20%, or 10 to 20% of the total weight percentage of propionyl groups.

In some embodiments of the present invention, the substrate is, the cellulose ester has from 5 to 57%, or from 10 to 57%, or from 15 to 57%, or from 20 to 57%, or from 25 to 57%, or from 30 to 57%, or from 35 to 57%, or from 40 to 57%, or from greater than 40 to 57%, or from 41 to 57%, or from 45 to 57%, or from 50 to 57%, or from 5 to 55%, or from 10 to 55%, or from 15 to 55%, or from 20 to 55%, or from 25 to 55%, or from 30 to 55%, or from 35 to 55%, or from 40 to 55%, or from greater than 40 to 55%, or from 41 to 55%, or from 45 to 55%, or from 50 to 55%, or from 5 to 50%, or from 10 to 50%, or from 15 to 50%, or from 20 to 50%, or from 25 to 50%, or from 30 to 50%, or from 35 to 50%, based on the total weight of the cellulose ester polymer or 40 to 50%, or greater than 40 to 50%, or 41 to 50%, or 45 to 50%, or 5 to 45%, or 10 to 45%, or 15 to 45%, or 20 to 45%, or 25 to 45%, or 30 to 45%, or 35 to 45%, or 40 to 45%, or greater than 40 to 45%, or 41 to 45%, or 5 to 35%, or 10 to 35%, or 15 to 35%, or 20 to 35%, or 25 to 35%, or 30 to 35%, or 5 to less than 32%, or 10 to less than 32%, or 15 to less than 32%, or 20 to less than 32%, or 25 to less than 32%, or 5 to 30%, or 10 to 30%, or 15 to 30%, or 20 to 30%, or 25 to 30% of the total weight percentage of butyryl groups.

In certain embodiments, the cellulose ester is a cellulose propionate butyrate or a cellulose acetate propionate butyrate, a combined level of propionyl (propionate) and butyryl as a percentage of the total polymer weight of 15% to 55%, or 15% to 50%, or 15% to 45%, or 15% to 40%, or 15% to 35%, or 15% to 30%, or 15% to 25%, or 15% to 20%, or 20% to 55%, or 20% to 50%, or 20% to 45%, or 20% to 40%, or 20% to 35%, or 20% to 30%, or 20% to 25%, or 25% to 55%, or 25% to 50%, or 25% to 45% or 25% to 40%, or 25% to 35%, or 25% to 30%, or 30% to 55%, or 30% to 50%, or 30% to 45%, or 30% to 40%, or 30% to 35%, or 35% to 55%, or 35% to 50%, or 35% to 45%, or 35% to 40%, 40% to 55%, or 40% to 50%, or 40% to 45%, or 40% to 55%, or 40% to 45%, or 45% to 55%, or 45% to 50%, or 50% to 55%.

The cellulose esters may be produced by any method known in the art. Examples of processes for producing cellulose esters are taught in Kirk-Othmer, encyclopedia of Chemical Technology, 5 th edition, volume 5, wiley-Interscience, new York (2004), pages 394-444. Cellulose, a raw material for the production of cellulose esters, is available in various grades and sources, such as from cotton linters, softwood pulps, hardwood pulps, corn fiber and other agricultural sources, and bacterial cellulose, among others.

One method of producing cellulose esters is to esterify cellulose by mixing it with a suitable organic acid, an acid anhydride and a catalyst. The cellulose is subsequently converted to a cellulose triester. Ester hydrolysis is then performed by adding a water-acid mixture to the cellulose triester, which can then be filtered to remove any gel particles or fibers. Water is then added to the mixture to precipitate the cellulose ester. The cellulose ester may then be washed with water to remove reaction by-products, followed by dehydration and drying.

The cellulose triester to be hydrolyzed may have three substituents independently selected from alkanoyl groups having 2 to 10 carbon atoms. Examples of cellulose triesters include cellulose triacetate, cellulose tripropionate, and cellulose tributyrate or mixed cellulose triesters such as cellulose acetate propionate and cellulose acetate butyrate. These cellulose esters can be prepared byMany methods are known to those skilled in the art. For example, cellulose esters can be prepared by reacting cellulose in a mixture of carboxylic acid and anhydride in a catalyst such as H ₂ SO ₄ Heterogeneous acylation in the presence. Cellulose triesters can also be prepared by homogeneous acylation of cellulose dissolved in a suitable solvent such as LiCl/DMAc or LiCl/NMP.

After esterification of the cellulose to a triester, a portion of the acyl substituents can be removed by hydrolysis or by alcoholysis to produce the type II cellulose ester. As noted above, the distribution of acyl substituents can be random or non-random depending on the particular process used. The cellulose ester of type II can also be prepared directly without hydrolysis by using a limited amount of acylating agent. This method is particularly useful when the reaction is carried out in a solvent that dissolves cellulose. All of these methods can be used to obtain the cellulose esters useful in the present invention.

The most common type of commercial cellulose esters are prepared by the initial acid-catalyzed heterogeneous acylation of cellulose to form cellulose triesters. After obtaining a homogeneous solution of the cellulose triester in the corresponding carboxylic acid, the cellulose triester is subsequently subjected to hydrolysis until the desired degree of substitution is obtained. After separation, a random type II cellulose ester is obtained. That is, the Relative Degrees of Substitution (RDS) at each hydroxyl group are approximately equal.

Some examples of Cellulose esters useful in various embodiments of the present invention can be prepared using techniques known in the art and are available from Eastman Chemical Company, kingsport, TN, U.S. A., e.g., eastman ™ cell Acetate Propionate CAP 482-20, eastman @ cell Acetate Propionate CAP141-20, eastman @ cell Acetate Butyrate CAB381-20, and cell Acetate Butyrate CAB 171-15. Some examples of common cellulose esters, with the falling ball viscosity values shown, are listed in table 1 below.

TABLE 1 common cellulose esters

CE numbering	Commercial CE material	Viscosity of the oil	Acetyl group weight%	Propionyl by weight%	Butyryl group weight%	OH% by weight
							1	CAP 482-20	20	1.3	48	0	2.0
2	CP520-7(CTP)	7	0	50	0	0.6
							3	CAB 381-20	20	13.5	0	37	1.7
4	CAP 141-3	3	29.1	14.7	0	2.3
							5	CAP 141-8	8	29.1	14.7	0	2.3
6	CAP 141-20	20	29.1	14.7	0	2.3
							7	VM230	20	0	38	0	7.8
8	CAP 202-29	29	24.48	18.07	0	3.3
							9	CA 398-3	3	39.8	0	0	3.6
10	CA 398-10	10	39.8	0	0	3.6
							11	CA 398-30	30	39.8	0	0	3.6
12	LA150	20	38	0	0	4.5

* CE Materials manufactured by Eastman Chemical Company.

In embodiments, the cellulose esters used in the present invention may also contain chemical functionality and are described herein as derivatized, modified, or functionalized cellulose esters. Functionalized cellulose esters can be made by reacting the free hydroxyl of the cellulose ester with a difunctional reactant having one linking group for grafting to the cellulose ester and one functional group that provides a new chemical group to the cellulose ester. Examples of such difunctional reactants include succinic anhydrides which are linked via an ester linkage and provide acid functionality; mercaptosilane linked through an alkoxysilane bond and providing mercapto functionality; and isocyanatoethyl methacrylate linked via urethane linkages and providing methacrylate functionality.

In one embodiment of the invention, functionalized cellulose esters are made by reacting free hydroxyl groups of a cellulose ester with a difunctional reactant to produce a cellulose ester having at least one functional group selected from the group consisting of unsaturation (double bond), carboxylic acid, acetoacetate, acetoacetimide ester (acetoacetate imide), mercapto, melamine, and long alkyl chains.

Bifunctional reactants for making cellulose esters containing long alkyl chain functionality are described in U.S. Pat. No. 5,750,677; which is incorporated by reference herein to the extent not inconsistent with the statements herein. In one embodiment, cellulose esters containing long alkyl chain functionality are made by reacting cellulose with an acylating agent in a carboxamide diluent or a urea-based diluent using a titanium-containing species. The cellulose ester containing long alkyl chain functionality may be selected from the group consisting of cellulose acetate hexanoate, cellulose acetate nonanoate, cellulose acetate laurate, cellulose palmitate, cellulose acetate stearate, cellulose nonanoate, cellulose hexanoate propionate, and cellulose nonanoate propionate.

In certain embodiments, the cellulose ester is a Cellulose Acetate Propionate (CAP) having a propionyl content of greater than 5% based on the total weight of the CAP polymer. In certain embodiments, the cellulose ester is a Cellulose Acetate Propionate (CAP) having a propionyl content of less than about 40%, based on the total weight of the CAP polymer.

In certain embodiments, the cellulose ester is a Cellulose Acetate Butyrate (CAB) having a butyryl content greater than 5% based on the total weight of the CAB polymer. In certain embodiments, the cellulose ester is a Cellulose Acetate Butyrate (CAB) having a butyryl content of less than 55% based on the total weight of the CAB polymer.

In some embodiments of the present invention, the substrate is, the cellulose ester has from 5 to 57%, or from 10 to 57%, or from 15 to 57%, or from 20 to 57%, or from 25 to 57%, or from 30 to 57%, or from 35 to 57%, or from 40 to 57%, or from greater than 40 to 57%, or from 41 to 57%, or from 45 to 57%, or from 50 to 57%, or from 5 to 55%, or from 10 to 55%, or from 15 to 55%, or from 20 to 55%, or from 25 to 55%, or from 30 to 55%, or from 35 to 55%, or from 40 to 55%, or from greater than 40 to 55%, or from 41 to 55%, or from 45 to 55%, or from 50 to 55%, or from 5 to 50%, or from 10 to 50%, or from 15 to 50%, or from 20 to 50%, or from 25 to 50%, or from 30 to 50%, or from 35 to 50%, based on the total weight of the cellulose ester polymer or 40 to 50%, or greater than 40 to 50%, or 41 to 50%, or 45 to 50%, or 5 to 45%, or 10 to 45%, or 15 to 45%, or 20 to 45%, or 25 to 45%, or 30 to 45%, or 35 to 45%, or 40 to 45%, or greater than 40 to 45%, or 41 to 45%, or 5 to 35%, or 10 to 35%, or 15 to 35%, or 20 to 35%, or 25 to 35%, or 30 to 35%, or 5 to less than 32%, or 10 to less than 32%, or 15 to less than 32%, or 20 to less than 32%, or 25 to less than 32%, or 5 to 30%, or 10 to 30%, or 15 to 30%, or 20 to 30%, or 25 to 30% of the total weight percent butyryl groups.

In certain embodiments, the cellulose ester is a cellulose propionate butyrate or a cellulose acetate propionate butyrate, the combined propionyl and butyryl content being in the following ranges as a percentage of the total weight of the polymer: 15% to 55%, or 15% to 50%, or 15% to 45%, or 15% to 40%, or 15% to 35%, or 15% to 30%, or 15% to 25%, or 15% to 20%, or 20% to 55%, or 20% to 50%, or 20% to 45%, or 20% to 40%, or 20% to 35%, or 20% to 30%, or 20% to 25%, or 25% to 55%, or 25% to 50%, or 25% to 45%, or 25% to 40%, or 25% to 35%, or 25% to 30%, or 30% to 55%, or 30% to 50%, or 30% to 45%, or 30% to 40%, or 30% to 35%, or 35% to 55%, or 35% to 50%, or 35% to 45%, or 35% to 40%, 40% to 55%, or 40% to 50%, or 40% to 45%, or 40% to 55%, or 40% to 45%, or 45% to 55%, or 50% to 55%, or 40% to 50%.

Any of the cellulose esters discussed above may also contain up to 10% residual hydroxyl units, preferably 0.5% to 5%.

In embodiments of the invention, the term "PBS polymer" is used interchangeably with polymeric aliphatic polyester ("PAP"), wherein PAP is a polymer comprising one or more C ₂ To C ₄ Residues of alkane diols and one or more C ₄ To C ₈ A residue of an alkyl dicarboxylic acid, or a polymerized aliphatic polyester comprising a residue of a ring-opened lactone. In embodiments, the PAP comprises C ₂ To C ₄ Residue of alkane diol and C ₄ To C ₆ Residues of alkyl dicarboxylic acids. In embodiments, the PAP comprises residues of ethylene glycol or 1, 4-butanediol and residues of succinic acid, glutaric acid, or adipic acid. In embodiments, the PAP comprises residues of ethylene glycol or 1, 4-butanediol and residues of succinic acid. In embodiments, the PAP is selected from poly (butylene succinate) or poly (ethylene succinate). In embodiments, the PAP is selected from poly (butylene adipate) or poly (ethylene adipate)). In embodiments, the PAP is poly (butylene succinate) (PBS). In another embodiment, the aliphatic polyester comprises a ring-opened residue of a lactone (cyclic ester), such as caprolactone. In embodiments, the PAP may be a copolymer. In embodiments, the PAP has a number average molecular weight (Mn) of greater than 2000, or 3000 or more, or 5000 or more, or 7000 or more, or 8000 or more, or 9000 or more, or 9500 or more, or 10000 or more. In embodiments, the PAP has a number average molecular weight (Mn) of 5000 to 20000, or 8000 to 15000, or 9000 to 12000. Molecular weights (and Mn) can be determined using Gel Permeation Chromatography (GPC) with a dichloromethane solvent with a refractive index detector and polystyrene standards. In one embodiment, PAP is a PAP having a molecular weight between 5000 and 20000; or 10000 to 20000; or Mn in the range of 15000 to 20000.

In embodiments of the invention, the PBS polymer (or PAP) can be any poly (butylene succinate) material. In embodiments, the PBS polymer (or PAP) can be selected from PBS random copolymers obtained from: succinic acid or succinate esters, 1, 4-butanediol and other dicarboxylic acids or alkylene glycols, such as adipic acid, glutaric acid, succinic acid with substituted side groups, suberic acid, 1, 3-propanediol and other substituted diols. Examples of poly (butylene succinate) materials include, but are not limited to, poly (butylene succinate-co-adipate) (PBSA), poly (butylene succinate-co-terephthalate), poly (butylene succinate-co-propylene succinate), poly (butylene succinate-co-methyl succinate), poly (butylene succinate-co-dimethyl succinate), poly (butylene succinate-co-phenyl succinate), and poly (butylene succinate) blends containing poly (adipate), poly (ethylene succinate), and/or poly (ethylene adipate). In one embodiment, the PBS polymer (or PAP) is poly (butylene succinate) (PBS).

In certain embodiments, the PAP has an MFR of less than 30, or less than 25, or less than 20, or less than 15, or less than 10, or less than 6, or about 5 or less, measured according to ASTM test method D1238 with a 2.16 kg load at 190 ℃. In embodiments, the PAP has an MFR of at least 0.5, or 1, or 2.

In embodiments, the PBS polymers (or PAPs) have MFRs (190 ℃,2.16 kg) in the range of 0.5-30, or 0.5-25, or 0.5-20, or 0.5-15, or 0.5-10, or 0.5-6, or 0.5-5. In embodiments, the PBS polymers (or PAPs) have an elongation at break of 100% or greater, or 150% or greater, or 200% or greater, or 250% or greater. In one embodiment, the cellulose ester composition contains at least one PBS polymer (or PAP) having an MFR (190 ℃,2.16 kg) of 10 or less and an elongation at break of 100% or more. In certain embodiments, the amount of such PBS polymer (or PAP) in the cellulose ester composition is from 0.5 to 40 weight%, or from 1 to 35 weight%, or from 2 to 30 weight%, or from 2 to 20 weight%, or from 2 to 10 weight%, or from 2.5 to 30 weight%, or from 5 to 25 weight%, or from 5 to 20 weight%, or from 5 to 15 weight%, or from 7 to 18 weight%, or from 8 to 12 weight%, based on the total cellulose ester composition. In certain embodiments, the composition contains at least one impact modifier, at least one monomeric plasticizer, in addition to the PBS polymer (or PAP), and the amount of PBS polymer (or PAP) in the cellulose ester composition is from 0.5 to 40 weight percent, or from 1 to 35 weight percent, or from 2 to 30 weight percent, or from 2 to 20 weight percent, or from 2 to 10 weight percent, or from 3 to 8 weight percent, or from 3 to 7 weight percent, or from 4 to 8 weight percent, based on the total cellulose ester composition; or 4 to 7 wt%.

In one embodiment, one or more impact modifiers may be included with the PBS polymer (or PAPs), and in certain embodiments, the impact modifier may be any polymeric material classified as an elastomer having a glass transition temperature (Tg) below room temperature. Tg can be measured, for example, according to ASTM D3418 using a TA 2100 Thermal analysis Instrument with a scan rate of 20 deg.C/min. Several classes of impact modifiers meet this description.

In one embodiment, the impact modifier may be selected from a class of materials referred to as modified polyolefins (or olefin copolymers). In this class, olefins are copolymerized with additional monomers that limit crystallization of the polymer, increase the amount of chains with Tg below room temperature and reduce the modulus below 500 MPa. Examples of modified olefins include Ethylene Methyl Acrylate (EMA) (examples include Elvaloy 4051, lotader 3410 and Lotader 8900), ethylene Butyl Acetate (EBA), ethylene Vinyl Acetate (EVA) (examples include Levamelt 500, levamelt 600, levamelt 700, levamelt 800, elvax 40W, evatane 28-40, evatane 40-55, evatane 18-150, bynel E418 and Bynel 3101), ethylene Ethyl Acetate (EEA), ethylene propylene diene monomer based Elastomers (EPDM) (examples include Royaltuftef 498) and ethylene propylene rubber Elastomers (EPR).

In one embodiment, the impact modifier may be a block copolymer, where at least one segment of the chain has a Tg below room temperature, referred to as a soft segment, and at least one segment of the chain has a Tg or Tm above room temperature, referred to as a hard segment. These block copolymers are also commonly referred to as thermoplastic elastomers (TPEs). Examples of block copolymers of this class include styrenic materials such as poly (styrene-butadiene-styrene) (SBS), poly (styrene-ethylene-butylene-styrene) (SEBS), and styrene-isoprene-rubber elastomers (SIS) (examples include Kraton G1657MS, kraton FG 1901G, and Kraton FG 1924G); thermoplastic Polyurethane (TPU) (examples include Elastolan 1170Z, estane 2355, estane ALR CL87A, and Estane ALR 72A); polyester-ether copolymers (examples include Ecdel 9966 and Hytrel 3078) or polyamide-ether copolymers (examples include Pebax 5533).

In one embodiment, the impact modifier may be selected from the class of materials prepared from emulsions known as core-shell impact modifiers. In one embodiment, the impact modifier is an MBS core-shell impact modifier, such as methacrylate-butadiene-styrene having a core made of butadiene-styrene copolymer and a shell made of methyl methacrylate-styrene copolymer. In another embodiment, the impact modifier is an acrylic core-shell impact modifier having a core made of an acrylic polymer (such as butyl acrylate or styrene-butyl acrylate) and a shell made of polymethyl methacrylate or styrene-methyl methacrylate copolymer.

In embodiments, the MBS impact modifier may comprise a graft polymer composition comprising 10 to 70 weight percent of a polymer or copolymer of butadiene and first a graft of methyl (meth) acrylate and a crosslinker and second a graft of styrene, and third a graft of methyl (meth) acrylate and an optional crosslinker.

Monomers suitable for polymerization with conjugated dienes, and preferably with butadiene, may include alkenyl aromatic compounds, and preferably vinyl aromatic compounds such as styrene, divinylbenzene, alpha-methylstyrene, vinyltoluene, hydrogenated styrene; lower (CZ-Cu) alkyl acrylates, such as ethyl acrylate, n-propyl acrylate, n-butyl acrylate, Z-methylbutyl acrylate, 3-methylbutyl acrylate, pentyl acrylate, n-hexyl acrylate, Z-ethylhexyl acrylate; lower (C2-C12) alkyl (meth) acrylates; acrylonitrile; an olefin; and the like; or a combination of any of the above.

Suitable crosslinking agents include divinylbenzene; di (meth) acrylates; diacrylates, such as diacrylates of mono-, di-or polyethylene glycols; (meth) acrylic acid esters thereof; divinyl sulfide; a divinyl ether; vinyl acrylate; vinyl (meth) acrylate; trivinyl benzene; trimethylolpropane; tri (meth) acrylates; triallyl cyanurate and triallyl isocyanurate.

In one embodiment, the MBS core shell impact modifier may comprise a copolymer of butadiene and styrene, and most preferably a terpolymer of butadiene, styrene and divinylbenzene. Although the relative amounts of the monomers making up the copolymer matrix (polymeric substrate) can vary, the butadiene component will typically constitute from about 30 to 100 parts by weight, the styrene component will constitute from 0 to about 70 parts by weight, and the divinylbenzene component will constitute from 0 to about 5 parts by weight, based on 100 parts by weight of the combination of butadiene, styrene, and divinylbenzene. In one embodiment, the copolymer matrix may comprise about 50 to about 90 parts by weight butadiene, about 10 to about 50 parts by weight styrene, and 0 to about 5 parts by weight divinylbenzene on the same basis, and most preferably about 65 to about 85 parts by weight butadiene, about 15 to about 35 parts by weight styrene, and about 0.5 to about 2.0 parts by weight divinylbenzene on the same basis.

Examples of methacrylate-butadiene-styrene core shell polymers are those described in, but not limited to, patents US 4,446,585, US 5,534,594 and US 6,331580. MBS core-shell impact modifiers are available as Kane Ace B564 from Kaneka, as Clearstrength from Arkema, as Metablen C and Metablen E from Mitsubishi Chemical, as Paraloid from Dow, and as Visiomer from Evonik.

In one embodiment of the present invention, the core shell impact modifier is an acrylic impact modifier comprising about 25 to 95 weight percent of a first elastomeric phase polymerized from a monomer system comprising about 75 to 99.8 weight percent (C1 to C6) alkyl acrylate, 0.1 to 5 weight percent of a crosslinking monomer, and 0.1 to 5 weight percent of a graft link monomer, and about 75 to 5 weight percent of a final rigid thermoplastic phase free of epoxy groups polymerized in the presence of the elastomeric phase.

Examples of useful acrylates are methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like. In some embodiments, the acrylates are n-butyl acrylate and ethyl acrylate.

Graft-linking monomers are defined as multi-ethylenically unsaturated monomers having both a high reactive double bond and a less reactive double bond, such that the high reactive double bond tends to polymerize during the first stage polymerization of the monomer, leaving the remaining double bond to polymerize during the next stage polymerization, and thereby graft-linking the first stage and second stage polymers. In some embodiments, the graft link monomers are allyl methacrylate, allyl acrylate, and diallyl maleate. In one embodiment, from 0.05 to 3 percent graft link monomer is present based on the first stage monomer system. It is also preferred that a crosslinking monomer is present, typically in an amount of about 0.05 to 3 weight percent based on the first stage monomer system, and is defined as a polyethylenically unsaturated monomer having at least two double bonds of approximately equal reactivity to cause crosslinking in the first stage polymerization. Examples of typical crosslinking monomers are 1, 3-butyl diacrylate, 1, 3-butyl dimethacrylate, divinyl benzene, and the like.

"epoxy functional" refers to epoxy units attached to the sides of the final stage polymer. In some embodiments, the epoxy functionality is incorporated into the final stage polymer by using an epoxy-containing monomer, such as glycidyl acrylate or glycidyl methacrylate, in the final stage monomer mixture.

Examples of acrylic core shell polymers are those described in patents US 3,448,173, US 3,655,825 and US 3,853,968 (but not limited thereto). Examples of suitable acrylic impact modifiers are Kane Ace ECO100 and M570 from Kaneka, durastrength from Arkema, elvaloy and Elvaloy HP from DuPont, metablen W from Mitsubishi Chemical, and Paraloid from Dow.

In one class of this embodiment, the impact modifier is an ABS core-shell impact modifier having a core made of butadiene-styrene copolymer and a shell made of acrylonitrile-styrene copolymer. Examples of ABS core shell impact modifiers include Blendex from Galata Chemicals and Elix from Elix Polymers.

In one class of this embodiment, the impact modifier is a silicone-acrylic core-shell impact modifier having a core made of a silicone-acrylic rubber and a shell made of a PMMA copolymer or a methyl methacrylate-styrene copolymer. Examples of silicone-acrylic core shell impact modifiers include Metablen S from Mitsubishi Chemical Company.

In one embodiment, the impact modifier has neutral acidity. It is believed that this will help prevent degradation of the cellulose ester during melt processing of the composition.

In one embodiment, the impact modifier may be a non-reactive impact modifier or a reactive impact modifier, or a combination of both. The impact modifier used may also improve the mechanical and physical properties of the cellulose ester composition.

In one embodiment where a non-reactive impact modifier is used, the impact modifier contains a first polymer chain segment that is more chemically or physically compatible with the cellulose ester than another polymer segment. In one embodiment, the first segment contains polar functional groups that provide compatibility with the cellulose ester, including but not limited to polar functional groups such as ethers, esters, amides, alcohols, amines, ketones, and acetals. Compatibility is defined as the first polymer segment preferentially interacting with the cellulose ester polymer relative to the second segment, and may refer to molecular-scale or micro-scale interactions. The first segment may be composed of the following oligomers or polymers: cellulose esters; a cellulose ether; polyoxyalkylenes such as polyoxyethylene, polyoxypropylene, polyoxybutylene; polyglycols, such as polyethylene glycol, polypropylene glycol, polybutylene glycol; polyesters, such as polycaprolactone, polylactic acid, aliphatic polyesters, aliphatic-aromatic copolyesters; polyacrylates and polymethacrylates; a polyacetal; polyvinylpyrrolidone; polyethylene-vinyl acetate; polyvinyl acetate; and polyvinyl alcohol. In one embodiment, the first segment is polyethylene-vinyl acetate; polyoxyethylene or polyvinyl alcohol.

In embodiments, the second segment can be a saturated or unsaturated hydrocarbon group, or contain both saturated and unsaturated hydrocarbon groups. The second segment may be an oligomer or a polymer. In one embodiment of the present invention, the second segment of the non-reactive impact modifier is selected from the group consisting of polyolefins, polydienes, polyaromatics, and copolymers. One example of a second segment of a polyaromatic is polystyrene. One example of a second segment of the copolymer is a styrene/butadiene copolymer.

The first and second segments of the non-reactive impact modifier may be diblock, triblock, branched, or comb-like structures. The weight average molecular weight (Mw) of the non-reactive impact modifier may be from about 300 to about 20,000 or from about 500 to about 10,000 or from about 1,000 to about 5,000. The non-reactive impact modifier may have a segment ratio of about 15 to about 85% polar first segment/about 15 to about 85% non-polar second segment.

Examples of non-reactive impact modifiers include, but are not limited to, ethoxylated alcohols, ethoxylated alkyl phenols, ethoxylated fatty acids, polyethylene-vinyl acetate, block polymers of propylene oxide and ethylene oxide, ethylene/propylene terpolymers, functionalized polyolefins, polyglycerol esters, polysaccharide esters, and sorbitan esters. An example of an ethoxylated alcohol is C ₁₁ -C ₁₅ Secondary alcohol ethoxylates, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether and C ethoxylated with ethylene oxide ₁₂ -C ₁₄ A natural straight chain alcohol. C ₁₁ -C ₁₅ Secondary alcohol ethoxylates are available as Dow Tergitol ^® 15S was obtained from the Dow Chemical Company. The polyoxyethylene cetyl ether and polyoxyethylene stearyl ether may be Brij ^® Product lines were obtained from ICI Surfactants. C ethoxylated with ethylene oxide ₁₂ -C ₁₄ The natural linear alcohol can be Genapol ^® Product line was obtained from Hoechst Celanese. Examples of ethoxylated alkylphenols include octylphenoxy poly (ethyleneoxy) ethanol and nonylphenoxy poly (ethyleneoxy) ethanol. Octylphenoxypoly (ethyleneoxy) ethanols as Igepal ^® The CA product line is available from Rhodia, and nonylphenoxypoly (ethyleneoxy) ethanol is available from Rhodia as the Igepal CO product line, or as Tergitol ^® NP was obtained from the Dow Chemical Company. The ethoxylated fatty acid may include polyethylene glycol monostearate or monolaurate, which may be in the form of Nopalcol ^® Product line was obtained from Henkel. The block polymer of propylene oxide and ethylene oxide may be as Pluronic ^® Product line was obtained from BASF. The polyglycerol ester may be in Drewpol ^® The product line was obtained from Stepan. The polysaccharide ester may be present as Glucopon ^® The product line was obtained from Henkel, which is an alkyl polyglucoside. The sorbitan ester may be in the form of Tween ^® Product line was obtained from ICI.

In another embodiment of the present invention, the non-reactive impact modifier may be synthesized in situ in the cellulose ester composition by reacting the cellulose ester compatible compound. These compounds may be, for example, telechelic oligomers, which are defined as prepolymers capable of entering further polymerization or other reactions through their reactive end groups. In one embodiment of the present invention, the in situ impact modifiers may have a higher weight average molecular weight (Mw) of about 10,000 to about 1,000,000.

In another embodiment of the present invention, the impact modifier may be reactive. The reactive impact modifier may comprise a polymer or oligomer compatible with one component of the composition and a functional group capable of reacting with another component of the composition. In embodiments, two types of reactive impact modifiers may be used. The first reactive impact modifier has a hydrocarbon chain that is compatible with the cellulose ester and also has a functional group that is reactive with the cellulose ester. Such functional groups include, but are not limited to, carboxylic acids, anhydrides, acid chlorides, epoxides, and isocyanates. Specific examples of this type of reactive impact modifier include, but are not limited to: long chain fatty acids, such as stearic acid (octadecanoic acid); long chain fatty acid chlorides such as stearoyl chloride (octadecanoyl chloride); long chain fatty acid anhydrides such as stearic anhydride (octadecanoic anhydride); epoxidized oils and fatty esters; styrene maleic anhydride copolymers; maleic anhydride grafted polypropylene; copolymers of maleic anhydride with olefins and/or acrylates, for example terpolymers of ethylene, acrylate and maleic anhydride; and copolymers of glycidyl methacrylate with olefins and/or acrylates, for example terpolymers of ethylene, acrylic acid esters and glycidyl methacrylate.

The reactive impact modifier may be obtained as follows: SMA from Sartomer/Cray Valley ^® 3000 styrene maleic anhydride copolymer, eastman G-3015 from Eastman Chemical Company ^® Maleic anhydride grafted Polypropylene, epolene from Westlake Chemical ^® E-43 maleic anhydride grafted Polypropylene, lotader from Arkema ^® Random terpolymer of MAH 8200 ethylene, acrylic ester and maleic anhydride, lotader ^® Random terpolymer of GMA AX 8900 ethylene, acrylate and glycidyl methacrylate and Lotarder ^® Random terpolymerization of GMA AX 8840 ethylene, acrylic ester, and glycidyl methacrylateA compound (I) is provided.

Reactive polyolefin impact modifiers are available as Lotader, fusabond, elvloy PTW, lotryl, elvaloy AC, interLoy.

The second type of reactive impact modifier has a polar chain that is compatible with cellulose esters and also has functional groups that are reactive with cellulose esters. Examples of these types of reactive impact modifiers include cellulose esters or polyethylene glycols having olefin or thiol functionality. Reactive polyethylene glycol impact modifiers with olefinic functionality include, but are not limited to, polyethylene glycol allyl ethers and polyethylene glycol acrylates. Examples of reactive polyethylene glycol impact modifiers having a thiol function include polyethylene glycol thiols. Examples of reactive cellulose ester impact modifiers include cellulose thioglycolate.

In embodiments of the invention, the amount of impact modifier in the cellulose ester composition may be from about 1 wt% to about 15 wt%, or from about 2 wt% to about 10 wt%, or from about 4 wt% to about 8 wt%, or from about 5 wt% to about 10 wt%, based on the weight of the cellulose ester composition. In certain embodiments, the cellulose ester composition comprises 55 to 98 weight percent of at least one cellulose ester, preferably CAP;1 to 30 wt% of at least one PBS polymer (or PAP), preferably PBS having an MFR (190 ℃,2.16 kg) of less than 25 and an elongation at break of 100% or more; and 1 to 15 weight percent of at least one impact modifier, preferably an acrylic core shell impact modifier. In embodiments containing an impact modifier, the CAP contains greater than 10%, or greater than 20%, or greater than 30%, or greater than 40%, or greater than 45% by weight propionyl groups.

In one embodiment, the cellulose ester composition is transparent, has a light transmission of at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, as measured according to ASTM D1003 using 3.2mm plaques after injection molding at a barrel set point of 249 ℃ and a residence time of 5 minutes. In certain embodiments, the polymer-based resin has a transmittance of 70% to 95%, or 75% to 95%, or 80% to 95%, or 85% to 95%, or 90% to 95%, or 70% to 90%, or 75% to 90%, or 80% to 90%, or 85% to 90%, measured according to ASTM D1003 using 3.2mm plaques after injection molding at a barrel set point of 249 ℃ and a residence time of 5 minutes. In one class of this embodiment, the cellulose ester composition comprising the PBS polymer (or PAP) has a percent haze of less than 10%. In embodiments, the cellulose ester composition comprising the PBS polymer (or PAP) has a percent haze of less than 8%, or less than 6%, or less than 5%.

In another embodiment, the Refractive Index (RI) of the PBS polymer (or PAP) is sufficiently close to that of the cellulose ester(s) to provide a composition with high transmission and low haze. In one embodiment, the PBS polymer (or PAP) has an RI of approximately 1.46 to 1.48 near the RI of the cellulose ester to provide a clear composition. In embodiments, the PBS polymer (or PAP) and cellulose ester component have a refractive index difference of about 0.006 to about-0.0006, RI (second component) -RI (first component) (e.g., RI of CE-PBS), and the blend has a percent transmission of at least 75%, and a haze of 10% or less, and more preferably 5% or less.

In embodiments of the invention, the amount of PBS polymer (or PAP) in the cellulose ester composition can be from about 0.5 wt% to about 40 wt%, or from about 1 wt% to about 35 wt%, or from 2 to 30 wt%, or from 2 to 20 wt%, or from 2 to 10 wt%, or from about 2.5 wt% to about 30 wt%, or from about 5 wt% to about 25 wt%, or from about 5 wt% to about 20 wt%, or from about 5 wt% to about 15 wt%, or from about 5 wt% to about 10 wt%, or from about 10 wt% to about 30 wt%, or from about 10 wt% to about 25 wt%, or from about 10 wt% to about 20 wt%, or from about 10 wt% to about 15 wt%, or from greater than 10 wt% to about 30 wt%, or from greater than 10 wt% to about 25 wt%, or from greater than 10 wt% to about 20 wt%, or from greater than 10 wt% to about 15 wt%, based on the weight of the cellulose ester composition. In embodiments, the composition contains at least one impact modifier and/or at least one monomeric plasticizer in addition to the PBS polymer (or PAP), and the amount of PBS polymer (or PAP) in the cellulose ester composition is 0.5 to 40 wt.%, or 1 to 35 wt.%, or 2 to 30 wt.%, or 2 to 20 wt.%, or 2 to 10 wt.%, or 3 to 8 wt.%, or 3 to 7 wt.%, or 4 to 8 wt.% of the total cellulose ester composition; or 4 to 7 wt%.

In another embodiment of the invention, the cellulose ester composition further comprises at least one additional polymeric component as a blend (with the cellulose ester) in an amount of from 5 to 95 weight percent based on the total cellulose ester composition. Suitable examples of additional polymeric components include, but are not limited to, nylon; a polyester; a polyamide; polystyrene; other cellulose esters, cellulose ethers; a polystyrene copolymer; styrene acrylonitrile copolymers; a polyolefin; a polyurethane; acrylonitrile butadiene styrene copolymers; poly (methyl methacrylate); an acrylic copolymer; poly (ether-imide); polyphenylene ether; polyvinyl chloride; polyphenylene sulfide; polyphenylene sulfide/sulfones (polyphenyleneene sulfides/sulfones); poly (ester-carbonates); a polycarbonate; polysulfones; polylactic acid; polysulfone ethers; and poly (ether-ketones) of aromatic dihydroxy compounds; or a mixture of any of the above polymers. The blends may be prepared by conventional processing techniques known in the art, such as melt blending or solution blending. In certain embodiments, the total amount of additional polymer compound (excluding the PBS polymer (or PAP)) is less than 25 wt.%, or less than 20 wt.%, or less than 15 wt.%, or less than 10 wt.%, or less than 5 wt.%, or absent, based on the total weight of the cellulose ester composition.

In one embodiment of the invention, the composition may contain a monomeric plasticizer in addition to the PBS polymer (or PAP) (and impact modifier). In embodiments, the monomeric plasticizer used in the present invention may be any monomeric plasticizer known in the art that can lower the glass transition temperature and/or melt viscosity of cellulose esters to improve melt processing characteristics. The monomeric plasticizer may be any monomeric plasticizer suitable for use with cellulose esters (which is added in addition to the PBS polymer (or PAP) and impact modifier contained in the composition). The monomeric plasticizer content should be lower than the normal (or typical) monomeric plasticizer content used in conventional/commercial cellulose esters; so that the composition has a higher Tg, good toughness and good flow than a fully plasticized cellulose ester composition. In embodiments, the monomeric plasticizer is present in an amount that does not significantly reduce the Tg of the cellulose ester composition as compared to a similar composition without the monomeric plasticizer. In embodiments, the change (e.g., decrease) in Tg due to inclusion of the monomeric plasticizer is no greater than 20%, or 15%, or 10%, or 5%, or 2%.

In one embodiment, the monomeric plasticizer is at least one selected from the group consisting of: aromatic phosphate ester plasticizers, alkyl phosphate ester plasticizers, dialkyl ether diester plasticizers, tricarboxylate plasticizers, polymeric polyester plasticizers, polyethylene glycol diester plasticizers, polyester resin plasticizers, aromatic diester plasticizers, aromatic triester plasticizers, aliphatic diester plasticizers, carbonate plasticizers, epoxidized ester plasticizers, epoxidized oil plasticizers, benzoate plasticizers, polyol benzoate plasticizers, adipate plasticizers, phthalate plasticizers, glycolate plasticizers, citrate plasticizers, hydroxy-functional plasticizers, or solid amorphous resin plasticizers.

In one embodiment of the present invention, the monomeric plasticizer may be selected from at least one of the following: triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, octyldiphenyl phosphate, diphenyldiphenyl phosphate, trioctyl phosphate, tributyl phosphate, diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, dibenzyl phthalate, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, and acetyl tri-n- (2-ethylhexyl) citrate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, or triethylene glycol dibenzoate.

In another embodiment of the present invention, the monomeric plasticizer may be selected from at least one of the following: an ester, comprising: (ii) (i) an acid residue comprising one or more of the following residues: phthalic acid, adipic acid, trimellitic acid, succinic acid, benzoic acid, azelaic acid, terephthalic acid, isophthalic acid, butyric acid, glutaric acid, citric acid, or phosphoric acid; and (ii) an alcohol residue comprising one or more residues of an aliphatic, cycloaliphatic, or aromatic alcohol containing up to about 20 carbon atoms.

In another embodiment of the present invention, the monomeric plasticizer may be selected from at least one of the following: an ester, comprising: (i) At least one acid residue selected from the group consisting of phthalic acid, adipic acid, trimellitic acid, succinic acid, benzoic acid, azelaic acid, terephthalic acid, isophthalic acid, butyric acid, glutaric acid, citric acid, and phosphoric acid; and (ii) at least one alcohol residue selected from the group consisting of aliphatic, cycloaliphatic, and aromatic alcohols containing up to about 20 carbon atoms.

In another embodiment of the present invention, the monomeric plasticizer may comprise an alcohol residue, wherein the alcohol residue is at least one selected from the group consisting of: stearyl alcohol, lauryl alcohol, phenol, benzyl alcohol, hydroquinone, catechol, resorcinol, ethylene glycol, neopentyl glycol, 1, 4-cyclohexanedimethanol, and diethylene glycol.

In another embodiment of the present invention, the monomeric plasticizer may be selected from at least one of the following: benzoates, phthalates, phosphates, arylene-bis (diaryl phosphate), and isophthalates. In another embodiment, the monomeric plasticizer comprises diethylene glycol dibenzoate, abbreviated herein as "DEGDB.

In another embodiment of the present invention, the monomeric plasticizer may be selected from the group consisting of C _2- C ₁₀ Diacid residues, such as malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and sebacic acid; and C _2- C ₁₀ Aliphatic compounds of diol residues.

In another embodiment, the monomeric plasticizer may comprise diol residues, which may be C below ₂ -C ₁₀ A residue of at least one of diols: ethylene glycol, diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediolAlcohols, 1, 4-butanediol, neopentyl glycol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 5-pentanediol, triethylene glycol and tetraethylene glycol.

In another embodiment of the present invention, the monomeric plasticizer comprises at least one of: resoflex ^® R296 plasticizer, resoflex ^® 804 plastocizer, SHP (sorbitol hexapropionate), XPP (xylitol pentapropionate), XPA (xylitol pentaacetate), GPP (glucose pentaacetate), GPA (glucose pentapropionate) and APP (arabitol pentapropionate).

In another embodiment of the invention, the monomeric plasticizer comprises one or more of the following: a) About 5 to about 95 weight percent C ₂ -C ₁₂ An organic ester of a carbohydrate, wherein the carbohydrate comprises from about 1 to about 3 monosaccharide units; and B) about 5 to about 95 weight percent C ₂ –C ₁₂ A polyol ester wherein the polyol is derived from C ₅ Or C ₆ A carbohydrate. In one embodiment, the polyol ester does not comprise or contain one or more polyol acetates.

In another embodiment, the monomeric plasticizer comprises at least one carbohydrate ester, and the carbohydrate portion of the carbohydrate ester is derived from one or more compounds selected from the group consisting of glucose, galactose, mannose, xylose, arabinose, lactose, fructose, sorbose, sucrose, cellobiose, cellotriose, and raffinose.

In another embodiment of the present invention, the monomeric plasticizer comprises at least one carbohydrate ester, and the carbohydrate portion of the carbohydrate ester comprises one or more of alpha-glucose pentaacetate, beta-glucose pentaacetate, alpha-glucose pentapropionate, beta-glucose pentapropionate, alpha-glucose pentabutyrate, and beta-glucose pentabutyrate.

In another embodiment, the monomeric plasticizer comprises at least one carbohydrate ester, and the carbohydrate portion of the carbohydrate ester comprises an α -anomer, a β -anomer, or a mixture thereof.

In another embodiment, the monomeric plasticizer may be selected from at least one of the following: propylene glycol dibenzoate, glycerol tribenzoate, diethylene glycol dibenzoate, triethylene glycol dibenzoate, dipropylene glycol dibenzoate, and polyethylene glycol dibenzoate.

In another embodiment of the present invention, the monomeric plasticizer may be a solid amorphous resin. These resins may contain some amount of aromatic or polar functionality and may reduce the melt viscosity of the cellulose ester. In one embodiment of the invention, the monomeric plasticizer may be a solid amorphous compound (resin), such as, for example, rosin; hydrogenated rosin; stabilized rosins, and their monofunctional alcohol esters or polyol esters; modified rosins including, but not limited to, maleic-and phenol-modified rosins and esters thereof; a terpene resin; a phenol-modified terpene resin; coumarin-indene resin; phenol resins (phenolic resins); alkylphenol-acetylene resins; and phenol-formaldehyde resins (phenol-formaldehyde resins).

In another embodiment of the present invention, the monomeric plasticizer is at least one monomeric plasticizer selected from the group consisting of: <xnotran> , , , , , , , , , , , , , , -2- , , , , , , , n- , , , , , , , , , , , , , , , -2- , -2- , , , , , N- , </xnotran>C ₁ -C ₂₀ Dicarboxylic acid esters, dimethyl adipate, dibutyl maleate, dioctyl maleate, resorcinol monoacetate, catechol esters, phenols, epoxidized soybean oil, castor oil, linseed oil, epoxidized linseed oil, other vegetable oils, other seed oils, difunctional glycidyl ethers based on polyethylene glycol, γ -valerolactone, alkyl phosphate esters, aryl phosphate esters, phospholipids, eugenol, cinnamyl alcohol, camphor, methoxyhydroxyacetophenone, vanillin, ethyl vanillin, 2-phenoxyethanol, glycol ethers, glycol esters, glycol ester ethers, polyglycol esters, glycol ethers, propylene glycol ethers, glycol esters, polypropylene glycol esters, acetylsalicylic acid, acetaminophen, naproxen, imidazole, triethanolamine, benzoic acid, benzyl benzoate, salicylic acid, 4-hydroxybenzoic acid, propyl 4-hydroxybenzoate, methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, butylated hydroxytoluene, butylated hydroxyanisole, sorbitol, piperazine, ethylene diamine, hexamethylenediamine, piperazine, and any combination thereof.

In embodiments, the amount of monomeric plasticizer in the cellulose ester composition may be in an amount of from greater than 0 to about 15 weight percent, based on the weight of the cellulose ester composition, e.g., depending on the type of cellulose ester used. In one embodiment, the amount may be up to about 15 weight percent, based on the weight of the cellulose ester composition. In another embodiment, the amount may be up to about 10 weight percent based on the weight of the cellulose ester composition. In another embodiment, the amount can be an amount of up to about 5 weight percent, based on the weight of the cellulose ester composition, or less than 5 weight percent, or up to about 4 weight percent, or less than about 3 weight percent, based on the weight of the cellulose ester composition.

In one embodiment of the invention, the cellulose ester composition may further comprise a plasticizer selected from one or more polyglycols (in addition to or in place of the monomeric plasticizer), such as polyethylene glycol, polypropylene glycol, and polybutylene glycol. These can be low molecular weight dimers and trimers to high molecular weight oligomers and polymers. In one embodiment, the weight average molecular weight (Mw) of the polyglycol may be from about 200 to about 2000.

In embodiments, it should be understood that the cellulose ester composition may contain materials that fall within the class of materials generally known or described herein for the purpose of being monomeric plasticizers, but are not considered monomeric plasticizers for use in the present invention, provided that the material is of a particular type or included in an amount that provides (or contributes) (in addition to the plasticizer function) other functions but has little effect (e.g., less than 1% or less than 0.5% change in these properties) on lowering the Tg or lowering the melt flow viscosity. For example, epoxidized soybean oil (e.g., vikoflex 7170) may be added in small amounts (e.g., 1 wt% or less based on the composition) to act as an acid scavenger to stabilize the composition, and although epoxidized oil or epoxidized soybean oil may generally be a class of monomeric plasticizers, such materials should not be considered monomeric plasticizers (if they do not contain other materials that act as plasticizers) and should be excluded from the scope of monomeric plasticizers specified (in accordance with various embodiments disclosed herein).

In embodiments, the composition is free of polyetherester compounds. In embodiments, the composition is free of adipic acid compounds. In embodiments, the composition is free of tall oil fatty acid esters. In embodiments, the composition is free of aromatic fatty acid esters. In embodiments, the composition is free of acylated phenolic-added fatty acid esters or diesters. In embodiments, the composition does not contain triethyl citrate.

In embodiments, the composition contains 0 to 2 wt.%, or 0 to 1.5 wt.%, or 0 to 1 wt.% fatty acid ester. In embodiments, the composition contains 0 to 2 wt.%, or 0 to 1.5 wt.%, or 0 to 1 wt.% of an epoxidized fatty acid ester, such as epoxidized soybean oil. In embodiments, the composition contains 0.1 to 2 wt.%, or 0.1 to 1.5 wt.%, or 0.1 to 1 wt.% of the epoxidized fatty ester. In embodiments, the composition contains 0.1 to 2 wt.%, or 0.1 to 1.5 wt.%, or 0.1 to 1 wt.% epoxidized soybean oil. In embodiments, the composition contains 0.1 to 2 weight percent, or 0.1 to 1.5 weight percent, or 0.1 to 1 weight percent of the epoxidized fatty acid ester and contains less than 5 weight percent of any other monomeric plasticizer. In embodiments, the composition contains 0.1 to 2 wt.%, or 0.1 to 1.5 wt.%, or 0.1 to 1 wt.% epoxidized soybean oil and contains less than 5 wt.% of any other monomeric plasticizer.

In certain embodiments, the cellulose ester composition comprises 65 to 99 wt% of one or more cellulose esters, 1 to 35 wt% of one or more PBS polymers (or PAPs), 1 to 35 wt% of one or more impact modifiers, 1 to 5 wt% of at least one monomeric plasticizer, and less than 10 wt% of all other components, based on the total weight of the cellulose ester composition. In certain embodiments, such other components do not include a polyetherester compound or an adipic acid compound. In certain embodiments, the cellulose ester composition is free of polyether ester compounds or camphor plasticizers.

In other embodiments of the present invention, the cellulose ester composition comprises at least one cellulose ester, at least one PBS polymer (or PAP), at least one impact modifier, and at least one monomeric plasticizer. In embodiments, the cellulose ester is CAP (e.g., CAP 482-20 from Eastman), the impact modifier is an acrylic core-shell impact modifier (e.g., kane Ace M570 impact modifier from Kaneka), the PBS polymer (or PAP) is poly (butylene succinate) (e.g., PBS designation C or D from table 2), and the monomeric plasticizer is dioctyl adipate (DOA), wherein the total amount of monomeric plasticizer is 5 wt.% or less, or less than 5 wt.% (e.g., 2 to less than 5 wt.%, or 2 to 4 wt.%) based on the total cellulose ester composition. In embodiments, the PBS polymer (or PAP), the impact modifier, and the monomeric plasticizer are present in amounts sufficient to provide a cellulose ester composition having a Tg of at least 110 ℃ or at least 120 ℃, good impact strength properties, good gate strength, and good creep (deformation under load). In embodiments, the PBS polymer (or PAP) is present in an amount of 2 to 10 wt.%, or 3 to 8 wt.%, or 3 to 7 wt.%; the impact modifier is present in an amount of 2 to 10 wt.%, or 4 to 8 wt.%; the monomeric plasticizer is present in an amount of 1 to 5 weight percent, or 1 to less than 5 weight percent, or 2 to 4 weight percent; all based on the total weight of the cellulosic composition. In embodiments, the combined total of PBS polymer (or PAP), impact modifier, and monomeric plasticizer is 10 to 18 weight percent, or 12 to 17 weight percent, or 13 to 16 weight percent, based on the total cellulose ester composition.

In another embodiment of the present invention, the composition is melt processable. Melt processability generally refers to the ability to thermally process the materials below their degradation temperature to obtain uniform pellets or plastic articles. For example, the composition can be melt extruded on a Werner & pflerder 30 mm twin screw extruder at a throughput of 35 lbs/hr with a screw speed of 250 rpm and a barrel temperature of 240 ℃ and/or injection molded on a Toyo 110 injection molding machine with a barrel temperature of 240 ℃ and a mold temperature of 160 ° f with little molecular weight reduction (e.g., MW reduction of less than 5% from initial MW) or color degradation (e.g., haze increase of less than 5% or transmittance decrease of less than 5% based on gauge or 0 to 100%).

In one embodiment of the invention, a melt processable cellulose ester composition is provided comprising 1 to 35 wt%, or 2.5 to 30 wt%, 5 to 15 wt% PBS polymer (or PAPs) and less than 5 wt% monomeric plasticizer, and a glass transition temperature (Tg) of at least 120 ℃ (measured as further described herein according to ASTM D3418 at 20 ℃/min) and notched izod impact strength values of greater than 80, or 100, or 125, or 150J/m (measured according to ASTM D256 at 23 ℃ on 3.2mm thick bars) and a spiral flow value of at least 38 centimeters (15 inches) when measured at a barrel temperature of 240 ℃ using the procedures described herein. Notched Izod impact strength tests were performed at 23 ℃ on 3.2mm thick bars after slitting according to ASTM method D256, conditioning at 23 ℃ and 50% RH for 48 hours on molded bars, unless otherwise specified.

Spiral flow was determined according to: a reciprocating screw injection molding machine was used having a 110 ton clamping force, a 32 mm screw diameter, equipped with a water cooled cold runner mold having a helical cavity measuring 0.50 "wide x 0.030" deep x 60.00 "long. The cavity was fed through a 3.5 "long cold sprue with a nominal 0.400" diameter and 3 degree taper, followed by a 1.0 "long cold runner with a 0.30" nominal diameter, followed by a 0.25 "wide x 0.030" thick x 0.10 "long rectangular gate. Variables controlled for the experimental range included resin drying, injection unit barrel temperature, mold temperature, initial injection speed, injection pressure limit, screw rotation speed and back pressure at screw retraction, injection time and cycle time. For each combination of variables, the response includes the actual melt temperature and the distance the melt travels in the helical cavity, excluding runners and gates. The injection process was allowed to stabilize at each set of conditions-typically 10 to 15 injections-and then 10 molded specimens were collected for the average reported run length. All materials were molded using pressure control, mold temperature with 120 ° f, initial injection speed of 1 in/s, injection unit pressure limit of 2000 psi, injection time of 5s, cycle time of 32 s, maximum buffer (maximum damping) of 0.2 ″, screw back-off rotation speed of 150 rpm, and screw back-off back pressure of 100 psi.

In one embodiment, the melt processable cellulose ester composition comprises, in addition to the PBS polymer (or PAP), from greater than 0 to 15 weight percent impact modifier, from greater than 0 to 15 weight percent monomeric plasticizer, and has a Tg of greater than 120 ℃. In one embodiment, the melt processable cellulose ester composition comprises from 1 to 8 wt.%, or from 1 to 5 wt.%, or from 1 to less than 5 wt.% of monomeric plasticizer in addition to the PBS polymer (or PAP) and has a Tg of greater than 110 ℃. In another embodiment, the melt processable cellulose ester composition comprises from greater than 0 to 15 weight percent impact modifier, from greater than 0 to 10 weight percent monomeric plasticizer, and has a Tg greater than 130 ℃. In yet another embodiment, the melt processable cellulose ester composition comprises from greater than 0 to 10 weight percent impact modifier, from greater than 0 to 10 weight percent monomeric plasticizer, and has a Tg greater than 140 ℃. In another embodiment, the melt processable cellulose ester composition comprises from greater than 0 to 10 weight percent impact modifier, from greater than 0 to 5 weight percent monomeric plasticizer, and has a Tg greater than 140 ℃. In one embodiment, the impact modifier is a core shell impact modifier. In one embodiment, the impact modifier is an acrylic core-shell impact modifier.

In embodiments of the invention, the polymer-based resin has a Tg of greater than 100 ℃, or greater than 110 ℃, or greater than 120 ℃. In certain embodiments, the polymer-based resin has a Tg of at least 120 ℃, or at least 125 ℃, or at least 130 ℃, or at least 135 ℃, or at least 140 ℃, or at least 145 ℃, or at least 150 ℃, or at least 155 ℃, or at least 160 ℃. In certain embodiments, the polymer-based resin has a Tg of 100 ℃ to 190 ℃, 100 ℃ to 185 ℃, 100 ℃ to 180 ℃, 100 ℃ to 175 ℃, 100 ℃ to 170 ℃, 110 ℃ to 190 ℃, 110 ℃ to 185 ℃, 115 ℃ to 190 ℃, 115 ℃ to 185 ℃, 120 ℃ to 190 ℃, 120 ℃ to 185 ℃, 125 ℃ to 190 ℃, 125 ℃ to 185 ℃, 130 ℃ to 190 ℃, 130 ℃ to 185 ℃, 135 ℃ to 190 ℃, 135 ℃ to 185 ℃, 140 ℃ to 190 ℃, 140 ℃ to 185 ℃, or 145 ℃ to 190 ℃.

In an embodiment of the invention, the polymer-based resin has a notched izod impact strength of at least 80J/m, or at least 90J/m, or at least 100J/m, or at least 110J/m, or at least 120J/m, or at least 130J/m, or at least 140J/m, or at least 150J/m, or at least 160J/m, or at least 170J/m, or at least 180J/m, or at least 190J/m, or at least 200J/m as measured according to ASTM D256 using a 3.2mm thick spline that has been subjected to 50% relative humidity for 48 hours at 23 ℃. In some embodiments of the present invention, the substrate is, the polymer-based resin has a composition as measured according to ASTM D256 at about 80J/m to about 500J/m, about 80J/m to about 400J/m, about 80J/m to about 300J/m, about 80J/m to about 200J/m, about 100J/m to about 500J/m, about 100J/m to about 400J/m, about 100J/m to about 300J/m, about 100J/m to about 200J/m, about 120J/m to about 500J/m, about 120J/m to about 400J/m, about 120J/m to about 300J/m, about 120J/m to about 200J/m, about 150J/m to about 500J/m, or a blend of the polymer and the polymer about 150J/m to about 400J/m, about 150J/m to about 300J/m, about 150J/m to about 200J/m, about 170J/m to about 500J/m, about 170J/m to about 400J/m, about 170J/m to about 300J/m, about 170J/m to about 200J/m, 180J/m to about 500J/m, about 180J/m to about 400J/m, about 180J/m to about 300J/m, about 180J/m to about 200J/m, 190J/m to about 500J/m, about 190J/m to about 400J/m, about 190J/m to about 300J/m, about 190J/m to about 200J/m, 200J/m to about 500J/m, about 200J/m to about 400J/m, about 400J/m to about 400J/m, about 170J/m to about 300J/m, or a notched izod impact strength in the range of about 200J/m to about 300J/m.

In an embodiment of the invention, the polymer-based resin has a gate impact strength of at least 80J/m, or at least 90J/m, or at least 100J/m, or at least 110J/m, or at least 120J/m, or at least 130J/m, or at least 140J/m, or at least 150J/m, or at least 160J/m, or at least 170J/m, or at least 180J/m, or at least 190J/m, or at least 200J/m, as measured according to the method described in the examples below. In certain embodiments, the polymer-based resin has an impact strength ranging from about 80J/m to about 300J/m, from about 80J/m to about 250J/m, from about 80J/m to about 200J/m, from about 100J/m to about 300J/m, from about 100J/m to about 250J/m, from about 100J/m to about 200J/m, from about 120J/m to about 300J/m, from about 120J/m to about 250J/m, from about 120J/m to about 200J/m, from about 150J/m to about 300J/m, from about 150J/m to about 250J/m, from about 150J/m to about 200J/m, from about 170J/m to about 300J/m, from about 170J/m to about 250J/m, from about 170J/m to about 200J/m, from 180J/m to about 300J/m, from about 180J/m to about 180J/m, from about 180J/m to about 200J/m, from about 190J/m to about 190J/m, from about 200J/m, or from about 190J/m, as measured according to about 190J/m as described in the methods described in the examples below.

In an embodiment of the invention, the polymer-based resin has a weld impact strength of at least 80J/m, or at least 90J/m, or at least 100J/m, or at least 110J/m, or at least 120J/m, or at least 130J/m, or at least 140J/m, or at least 150J/m, or at least 160J/m, or at least 170J/m, or at least 180J/m, or at least 190J/m, or at least 200J/m, as measured according to the method described in the examples below. In some embodiments of the present invention, the substrate is, the polymer-based resin has a composition of matter at about 80J/m to about 300J/m, about 80J/m to about 250J/m, about 80J/m to about 200J/m, about 100J/m to about 300J/m, about 100J/m to about 250J/m, about 100J/m to about 200J/m, about 120J/m to about 300J/m, about 120J/m to about 250J/m, about 120J/m to about 200J/m, about 150J/m to about 300J/m, about 150J/m to about 250J/m, a glass transition temperature, and a glass transition temperature as measured according to the method described in the examples below a weld impact strength in a range of about 150J/m to about 200J/m, about 170J/m to about 300J/m, about 170J/m to about 250J/m, about 170J/m to about 200J/m, 180J/m to about 300J/m, about 180J/m to about 250J/m, about 180J/m to about 200J/m, 190J/m to about 300J/m, about 190J/m to about 250J/m, about 190J/m to about 200J/m, 200J/m to about 300J/m, about 200J/m to about 250J/m.

In certain embodiments of the invention, a 3.2mm thick plaque of polymer-based resin exhibits ductile failure as defined in section X1.8 of ASTM D3763 when passed the instrumented impact test according to ASTM D3763.

In an embodiment of the invention, the polymer-based resin has a flexural modulus of greater than 1600 MPa as measured according to ASTM D790 using 3.2mm thick bars that have been subjected to 50% relative humidity at 23 ℃ for 48 hours. In certain embodiments, the polymer-based resin has a flexural modulus of at least 1700, at least 1800, at least 1900 MPa, at least 2000 MPa, at least 2100 MPa, at least 2200 MPa, at least 2300MPa, or at least 2400 MPa as measured according to ASTM D790 using 3.2mm thick splines that have been subjected to 50% relative humidity at 23 ℃ for 48 hours. In certain embodiments, the polymer-based resin has a flexural modulus in a range of from about 1600 to about 3000 MPa, from about 1700 to about 3000 MPa, from about 1800 to about 3000 MPa, from about 1900 to about 3000 MPa, from about 2000 to about 3000 MPa, from about 2100 to about 3000 MPa, from about 2200 to about 3000 MPa, from about 2300 to about 3000 MPa, from about 2400 to about 3000 MPa, or from about 2500 to about 3000 MPa, as measured according to ASTM D790 using 3.2mm thick splines that have been subjected to 50% relative humidity for 48 hours at 23 ℃. In certain embodiments, the polymer-based resin has a flexural modulus in a range of from about 1600 to about 2500 MPa, from about 1700 to about 2500 MPa, from about 1900 to about 2800 MPa, or from about 1900 to about 3000 MPa, as measured according to ASTM D790 using 3.2mm thick splines that have been subjected to 50% relative humidity for 48 hours at 23 ℃.

In certain embodiments of the invention, the cellulose ester composition contains from 2.5 wt% to 30 wt% PBS polymer (or PAP), based on the total weight of the cellulose ester composition, having a Tg value greater than 120 ℃, a notched izod impact value greater than 80, or 100, or 125, or 150, or 175, or 200J/m, and a light transmission value greater than 80%, or at least 85%, or at least 90%, as measured according to ASTM D1003 using a 3.2mm plate after injection molding at a barrel set point of 249 ℃ and a residence time of 5 minutes.

One problem that can occur when melt processing cellulose esters containing low levels of monomeric plasticizer on a screw plasticizing injection molding machine is that the screw can be difficult to retract smoothly, resulting in poor material feed and a "squeak". It has been surprisingly found that the addition of PBS polymers (or PAPs) according to embodiments of the present invention can eliminate these problems during injection molding.

In certain embodiments of the invention, the cellulose ester composition contains from 2.5 wt% to 30 wt% of a PBS polymer (or PAP), based on the total weight of the cellulose ester composition, has a Tg value greater than 120 ℃, a notched izod impact strength value greater than 80, or 100, or 125, or 150, or 175, or 200J/m, and has no squeaking or screw back-off problems during injection molding at a barrel set point of 249 ℃.

In certain embodiments of the invention, the cellulose ester composition contains from 2.5 wt% to 30 wt% of a PBS polymer (or PAP) based on the total weight of the cellulose ester composition, has a Tg value greater than 120 ℃, a notched izod impact value greater than 150 or 200J/m, and a light transmission value greater than 80%, or at least 85%, or at least 90%, measured according to ASTM D1003 using a 3.2mm plaque after injection molding at a barrel set point of 249 ℃ and a residence time of 5 minutes.

In certain embodiments of the invention, a 3.2mm thick plaque containing from 2.5 to 30 weight percent of a PBS polymer (or PAP), based on the total weight of the cellulose ester composition, exhibits ductile failure as defined in section X1.8 of ASTM D3763 when passed the instrumented impact test according to ASTM D3763, and has a Tg value greater than 120 ℃.

In another embodiment of the present invention, the cellulose ester composition further comprises at least one additive selected from the group consisting of antioxidants, heat stabilizers, mold release agents, antistatic agents, brighteners, colorants, flow aids, processing aids, anti-fog additives, minerals, UV stabilizers, lubricants, chain extenders, nucleating agents, reinforcing fillers, wood or powder fillers, glass fibers, carbon fibers, flame retardants, dyes, pigments, colorants, additional resins, and combinations thereof.

In certain embodiments, the cellulose ester composition comprises a stabilizer selected from a secondary antioxidant, an acid scavenger, or a combination thereof, in addition to PAP (discussed herein), e.g., PBS, impact modifier, and monomer plasticizer. In certain embodiments, the cellulose ester composition comprises, in addition to PAP (discussed herein), e.g., PBS, impact modifier, and monomeric plasticizer, about 0.1 to about 0.8 wt.% of a second antioxidant, based on the total weight of the composition. In certain embodiments, the cellulose ester composition comprises, in addition to PAP (discussed herein), e.g., PBS, impact modifier, and monomeric plasticizer, from about 0.2 to about 2.0 wt% of an acid scavenger, based on the total weight of the composition. In one embodiment, the cellulose ester composition comprises, in addition to PAP (discussed herein), e.g., PBS, and optionally, impact modifier and/or monomer plasticizer, about 0.1 to about 0.8 wt.% of the second antioxidant and about 0.2 to about 2.0 wt.% of the acid scavenger, based on the total weight of the composition. In one embodiment, the second antioxidant is 3, 9-bis (2, 4-di-tert-butylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane. In one embodiment, the acid scavenger is an epoxidized fatty acid ester. In one embodiment, the cellulose ester composition further comprises a salt stabilizer, for example in the range of from about 0.1 to about 0.5 weight percent based on the total weight of the composition. In one embodiment, in addition to the cellulose ester, PAP, e.g., PBS, and stabilizer (discussed herein), the cellulose ester composition contains less than 10 wt.%, or less than 8 wt.%, or less than 5 wt.%, or less than 2 wt.% of any other component in total, based on the total weight of the composition.

In another embodiment of the present invention, a process for producing a cellulose ester composition is provided. The method comprises contacting at least one cellulose ester, at least one PBS polymer (or PAP), at least one impact modifier, and a monomeric plasticizer. Cellulose esters, impact modifiers, monomeric plasticizers, and PBS polymers (or PAPs) are previously discussed in this disclosure. In one embodiment, the cellulose ester, PBS polymer (or PAPs), impact modifier, and monomeric plasticizer may be mixed in any order of addition.

In another embodiment of the present invention, there is provided a process for producing a cellulose ester composition comprising: a) Mixing at least one PBS polymer (or PAP), at least one cellulose ester, at least one impact modifier, and a monomeric plasticizer for a sufficient time and temperature to disperse the PBS polymer (or PAP) to produce a cellulose ester composition. Sufficient temperature is defined as the flow temperature of the cellulose ester, which is typically about 50 ℃ above the Tg of the cellulose ester. In another embodiment, the temperature is about 80 ℃ above the Tg of the cellulose ester. In embodiments, the upper limit of the mixing temperature is defined by the processing temperature of the PBS polymer (or PAP) and the lower limit is defined by the maximum use temperature of the cellulose ester composition.

The efficiency of mixing two or more viscoelastic materials may depend on the viscosity ratio of the viscoelastic materials. In one embodiment, for a given mixing equipment and shear rate range, the viscosity ratio of the dispersed phase (PBS polymer (or PAP)) and the continuous phase (cellulose ester) should be within specified limits for obtaining sufficient particle size.

In embodiments, the mixing of the PBS polymer (or PAPs), the cellulose ester, the impact modifier, and the monomeric plasticizer and any additives may be accomplished by any method known in the art sufficient to disperse the PBS polymer (or PAPs), the impact modifier, the monomeric plasticizer, and the additives into the cellulose ester. Examples of mixing equipment include, but are not limited to, banbury mixers, brabender mixers, roll mills, and extruders (single or twin screw). The shear energy during mixing depends on the combination of equipment, blade design, rotational speed (rpm) and mixing time. The shear energy should be sufficient to disperse the PBS polymer (or PAP) and optional impact modifier throughout the cellulose ester.

In embodiments, the cellulose ester, PBS polymer (or PAP), impact modifier, monomeric plasticizer, and additives may be combined in any order during the process. In one embodiment, the cellulose ester is premixed with the PBS polymer (or PAP), the impact modifier, and the monomeric plasticizer. The cellulose ester containing the PBS polymer (or PAP), impact modifier, and monomeric plasticizer is then mixed with additives. In another embodiment of the present invention, when a reactive impact modifier is used, the reactive impact modifier may be first mixed with the cellulose ester and then the other components added.

The composition of the invention can be used as a molded plastic part or a solid plastic object. The composition is suitable for any application where a hard clear plastic is desired. Examples of such components include disposable knives, forks, spoons, trays, cups, straws and eyeglass frames, toothbrush handles, toys, automobile decorations, tool handles, camera components, components of electronic equipment, razor components, ink pen containers (ink pen containers), disposable syringes, bottles, and the like. In one embodiment, the compositions of the present invention are useful as plastics, films, fibers, including melt spun fibers and solvent spun fibers, and sheets. In one embodiment, the composition can be used as a plastic to make bottles, bottle caps, cosmetic packages, eyeglass frames, tableware, disposable tableware, tableware handles, shelving, shelf dividers, electronic equipment housings, electronic equipment cases, computer monitors, printers, keyboards, pipes, automotive parts, automotive upholstery, automotive trim, signs, thermoformed letters, siding, toys, thermally conductive plastics, lenses, tools, tool handles, utensils. In another embodiment, the compositions of the present invention are suitable for use as films, sheets, fibers, molded articles, medical devices, packaging, bottles, bottle caps, eyeglass frames, tableware, disposable tableware, tableware handles, shelving, shelf dividers, furniture components, electronic equipment housings, electronic equipment cases, computer monitors, printers, keyboards, tubing, toothbrush handles, automotive parts, automotive upholstery, automotive trim, signs, outdoor signs, skylights, multilayer films, thermoformed letters, wall panels, toys, toy parts, thermally conductive plastics, lenses and frames, tools, tool handles and utensils, health care supplies (heatcard offers), commercial food service products, boxes, films for graphic arts applications, and plastic films for plastic glass laminates.

The cellulose ester compositions are useful for forming fibers, films, molded articles, and sheets. The method of forming the cellulose ester composition into fibers, films, molded articles and sheets can be according to methods known in the art. Examples of potential molded articles include, but are not limited to: medical devices, medical packaging, health products, commercial food service products, such as dinner plates, cups and storage boxes, bottles, food processors, mixers and mixing bowls, utensils, water bottles, crispers (cans), washing machine front panels, vacuum cleaner parts and toys. Other potential molded articles may include lenses and frames.

The invention further relates to articles comprising one or more films and/or sheets comprising the cellulose ester compositions described herein. In embodiments, the films and/or sheets of the present invention can have any thickness that is apparent to any person of ordinary skill in the art.

The present invention further relates to one or more films and/or sheets as described herein. Methods of forming the cellulose ester composition into one or more films and/or sheets can include methods known in the art. Examples of one or more films and/or sheets of the present invention include, but are not limited to, one or more extruded films and/or sheets, calendered films and/or sheets, compression molded films and/or sheets, solution cast films and/or sheets. Methods of making films and/or sheets include, but are not limited to, extrusion, calendering, compression molding, wet block processing (wet block processing), dry block processing (dry block processing), and solution casting.

The present invention further relates to a molded article as described herein. Methods of forming the cellulose ester composition into a molded article may include methods known in the art. Examples of molded articles of the present invention include, but are not limited to, injection molded articles, extrusion molded articles, injection blow molded articles, injection stretch blow molded articles, and extrusion blow molded articles. Methods of making molded articles include, but are not limited to, injection molding, extrusion, injection blow molding, injection stretch blow molding, and extrusion blow molding. The process of the present invention may comprise any blow molding process known in the art including, but not limited to, extrusion blow molding, extrusion stretch blow molding, injection blow molding and injection stretch blow molding.

The present invention includes any injection blow molding manufacturing method known in the art. Although not limited thereto, a typical description of an Injection Blow Molding (IBM) manufacturing method involves: 1) Melting the composition in a reciprocating screw extruder; 2) Injecting the molten composition into an injection mold to form a partially cooled tube (i.e., a preform) that is closed at one end; 3) Moving the preform into a blow mould having the desired finished shape surrounding the preform and closing the blow mould surrounding the preform; 4) Blowing air into the preform to stretch and expand the preform to fill the mold; 5) Cooling the molded article; 6) The article is ejected from the mold.

The present invention includes any injection stretch blow molding manufacturing process known in the art. Although not limited thereto, a typical description of an Injection Stretch Blow Molding (ISBM) manufacturing process involves: 1) Melting the composition in a reciprocating screw extruder; 2) Injecting the molten composition into an injection mold to form a partially cooled tube (i.e., a preform) that is closed at one end; 3) Moving the preform into a blow mould having the desired finished shape surrounding the preform and closing the blow mould surrounding the preform; 4) Stretching the preform using an internal stretch rod and blowing air into the preform to stretch and expand the preform to fill the mold; 5) Cooling the molded article; 6) The article is ejected from the mold.

The present invention includes any extrusion blow molding manufacturing process known in the art. Although not limited thereto, typical descriptions of extrusion blow molding manufacturing methods include: 1) Melting the composition in an extruder; 2) Extruding the molten composition through a die to form a tube (i.e., a parison) of molten polymer; 3) Clamping a mold having the desired finished shape around the parison; 4) Blowing air into the parison to stretch and expand the extrudate to fill the mold; 5) Cooling the molded article; 6) Ejecting the article from the mold; and 7) removing excess plastic (commonly referred to as flash) from the article.

In certain aspects, articles useful for acoustic applications are provided that can comprise any of the cellulose ester compositions disclosed herein. In certain embodiments, the acoustic article contains a cellulose ester composition comprising at least one cellulose ester and at least one PBS polymer (or PAP). In embodiments, the cellulose ester is selected from CAP or CAB, and the PBS polymer (or PAP) is present in an amount of about 1 to 25 wt.%, or about 2 to 20 wt.%, or about 2 to 15 wt.%, or about 2 to 10 wt.%, based on the total composition.

In certain embodiments, the acoustic article comprises a cellulose ester composition comprising at least one cellulose ester, at least one PBS polymer (or PAP), and at least one impact modifier (as described herein). In embodiments, the cellulose ester is selected from CAP or CAB; the PBS polymer (or PAP) (e.g., PBS) is present in an amount of about 1 to 25 wt.%, or about 2 to 20 wt.%, or about 2 to 15 wt.%, or about 2 to 10 wt.%, based on the total composition; and the impact modifier is present in an amount of about 1 to 25 wt.%, or about 2 to 20 wt.%, or about 2 to 15 wt.%, or about 2 to 10 wt.%, based on the total composition. In embodiments, the impact modifier is a core-shell impact modifier, for example an acrylic core-shell impact modifier, such as M-570.

In certain embodiments, the acoustic article comprises a cellulose ester composition comprising at least one cellulose ester, at least one PBS polymer (or PAP), and at least one monomeric plasticizer (as described herein). In embodiments, the cellulose ester is selected from CAP or CAB; the PBS polymer (or PAP) (e.g., PBS) is present in an amount of about 1 to 25 wt.%, or about 2 to 20 wt.%, or about 2 to 15 wt.%, or about 2 to 10 wt.%, based on the total composition; and the monomeric plasticizer is present in an amount of about 0.1 to 8 weight percent, or about 1 to 6 weight percent, or about 1 to 5 weight percent, or about 1 to less than 5 weight percent, or about 2 to 4 weight percent, based on the total composition. In embodiments, the monomeric plasticizer is an adipate monomeric plasticizer, such as DOA.

In certain embodiments, the acoustic article comprises a cellulose ester composition comprising at least one cellulose ester, at least one PBS polymer (or PAP), at least one impact modifier (as described herein), and at least one monomeric plasticizer (as described herein). In embodiments, the cellulose ester is selected from CAP or CAB; the PBS polymer (or PAP) (e.g., PBS) is present in an amount of about 1 to 25 wt.%, or about 2 to 20 wt.%, or about 2 to 15 wt.%, or about 2 to 10 wt.%, based on the total composition; the impact modifier is present in an amount of about 1 to 25 wt.%, or about 2 to 20 wt.%, or about 2 to 15 wt.%, or about 2 to 10 wt.%, based on the total composition; and the monomeric plasticizer is present in an amount of about 0.1 to 8 weight percent, or about 1 to 6 weight percent, or about 1 to 5 weight percent, or about 1 to less than 5 weight percent, or about 2 to 4 weight percent, based on the total composition. In embodiments, the impact modifier is a core-shell impact modifier, for example an acrylic core-shell impact modifier, such as M-570, and the monomeric plasticizer is an adipate monomeric plasticizer, for example DOA.

In certain embodiments, the cellulose ester composition provides an acoustic article with improved vibration (and/or sound) damping compared to similar articles made from other thermoformable plastics (having one or more other similar physical properties), such as ABS, PC, polyester, or nylon. In embodiments, the article has a lower Total Harmonic Distortion (THD) than a similar article made from other such thermoformable plastics. In embodiments, the lower THD may be in the form of a lower average THD in a frequency range of 20 Hz to 20KHz, or 20 Hz to 10KHz, or 100 Hz to 10KHz, or 20 Hz to 500 Hz, or 3000 Hz to 20KHz, or 3000 Hz to 10KHz, as compared to a similar article made from other such thermoformable plastics. In embodiments, when comparing the highest THD peak in the THD plot as a function of frequency for a cellulose ester composition article compared to a similar article made from other such thermoformable plastics, the lower THD may be in the form of a lower THD peak, the frequency being in the frequency range of 20 Hz to 20KHz, or 20 Hz to 10KHz, or 20 Hz to 500 Hz, or 3000 Hz to 20KHz, or 3000 Hz to 10 KHz.

In certain embodiments, articles (made from the cellulose ester compositions described herein) have a Total Harmonic Distortion (THD) as measured by known methods of less than 0.3% in the frequency range of 20 to 500 Hz, or less than 0.2% in the frequency range of 3 to 10KHz, or less than 0.6% in the frequency range of 100 Hz to 10KHz or 100 Hz to 20 KHz.

In certain embodiments, a cellulose ester composition is provided having high vibration damping properties comprising a CAP, such as CAP 482-20 (from Eastman Chemical Company), and a combination of an impact modifier and a PBS polymer (or PAP), wherein the composition contains 2 to 15 wt.%, or 3 to 10 wt.%, or 4 to 8 wt.% of an impact modifier as described herein, such as an acrylic core shell impact modifier, such as M-570, and also contains 2 to 15 wt.%, or 3 to 10 wt.%, or 4 to 8 wt.% of a PBS polymer (or PAP) (as described herein).

In certain embodiments, a cellulose ester composition having high vibration damping properties is provided comprising a CAP, such as CAP 482-20 (from Eastman Chemical Company), and a combination of an impact modifier, a PBS polymer (or PAP), and a monomeric plasticizer, wherein the composition contains 2 to 15 wt.%, or 3 to 10 wt.%, or 4 to 8 wt.% of an impact modifier as described herein, such as an acrylic core shell impact modifier, such as M-570; also contains from 2 to 15 wt.%, or from 3 to 10 wt.%, or from 4 to 8 wt.% of a PBS polymer (or PAP) (as described herein); and further contains from 2 to 6 wt.%, or from 2 to 5 wt.%, or from 2 to less than 5 wt.%, or from 2 to 4 wt.% of a monomeric plasticizer as described herein, for example a DOA monomeric plasticizer. In embodiments, the cellulose ester composition contains from 4 to 8 weight percent of an impact modifier as described herein, for example an acrylic core shell impact modifier, such as M-570; and further contains 4 to 8 wt% PBS polymer (or PAP) (as described herein); and further contains from 2 to less than 5 wt%, or from 2 to 4 wt% of a monomeric plasticizer as described herein, for example a DOA monomeric plasticizer.

In embodiments, the cellulose ester compositions having high (or improved) vibration (or sound) damping may also have one or more of the other physical properties described herein. In embodiments, the one or more other physical properties are selected from relatively high Tg (e.g., 110 ℃, or 120 ℃ or higher Tg), high modulus, good impact properties, and good resistance to deformation under load (these properties are described in more detail herein).

In embodiments, the cellulose ester composition has excellent vibration damping properties, high flexural modulus, and excellent impact resistance, and can be suitably used for manufactured goods, such as audio equipment, electric appliances, construction/building materials, and industrial equipment, or parts or housings thereof, by using various mold processing methods, such as injection molding, extrusion molding, or thermoforming. Further, since the cellulose ester composition of the present invention has a relatively high flexural modulus, excellent vibration damping properties and the ability to sufficiently maintain its shape, the cellulose ester composition can be used in manufactured products intended to be lightweight for vehicles such as automobiles, railway vehicles and airplanes, or parts or housings thereof.

The application of the cellulose ester composition of the present invention to manufactured articles such as audio equipment, electric appliances, vehicles, construction/building materials and industrial equipment, or parts or housings thereof can be appropriately set depending on the method of manufacturing the parts, housings, devices and equipment, applied parts (applied parts) and intended use, and the composition can be used according to the conventional methods in the art. In other words, finished products such as audio equipment, electric appliances, vehicles, construction/building materials and industrial equipment, or parts or housings thereof can be obtained by molding the cellulose ester resin composition of the present invention according to a known method.

In embodiments, the cellulose ester resin composition of the present invention can be used as a material for a housing of an audio device for speakers, televisions, radio cassette players (radio cassette players), earphones, audio components, microphones, and the like; as materials for parts and housings of electric appliances having an electric motor, other electric tools such as electric drills and electric drivers, electric appliances having a cooling fan such as computers, projectors, servers and POS systems, washing machines, clothes dryers, air conditioning indoor units, sewing machines, dish washers, fan heaters, multifunction copiers, printers, scanners, hard disk drives, cameras, and the like; materials used as parts and housings of electric appliances containing vibration sources for electric toothbrushes, electric shavers, massage machines, and the like; materials used for a generator, a gas generator, and the like as components and a housing of an electric appliance having a motor; materials used for refrigerators, vending machines, outdoor air conditioners, dehumidifiers, and household power generators as parts and housings of electric appliances having compressors; materials used as automobile parts are used for interior materials such as instrument panels (dash boards), instrument panels, floors, doors, and ceilings, and materials related to engines such as oil pans, front covers, and deck lids; materials used as parts of railway vehicles for interior materials such as floors, walls, side panels, ceilings, doors, chairs and tables, housings or parts of areas related to engines, various protective covers, and the like; as materials for aircraft parts, interior materials such as floors, walls, side panels, ceilings, chairs and tables, housings or parts in engine-related parts, and the like; materials for parts of ships used for housings or wall materials of engine rooms, housings or wall materials of instrument measurement rooms; as building materials for walls, ceilings, floors, partitions, sound-insulating walls, shutters, curtain rails, ducts, stairs, doors, etc.; materials used as parts of industrial equipment are used for core shooters (shooters), elevators (elevators), escalators, conveyors, tractors, bulldozers, mowers, and the like.

In embodiments, acoustic articles (e.g., articles with high vibration damping or low THD) may be selected from integrated audio devices, including speakers in automobiles, televisions, and smart phones; free standing speakers (wired or wireless), home theater systems, including soundbars, bass speakers, and televisions (under televisions); smart speakers, including WiFi streaming, and virtual personal assistants (vpars); and earphones, earbuds, and other wearable speakers. In embodiments, the acoustic article may also be a component or part of any of these devices, such as a housing, an accessory, a speaker assembly, a microphone assembly, a headband, a wristband, a clip, a handle, and the like.

In embodiments, the article comprising the cellulose ester composition may be a wearable article or body contacting article that generates sound or is subjected to vibration, and may be selected from an eyeglass frame, an eyeglass lens, a sunglass frame, a sunglass lens, goggles, a wearable electronics, headphones, an earplug, a watch, a personal device, a personal electronic device, a medical package, a health care item, a personal protective device, a security device, a water sports item, or a component thereof. In one embodiment, the article comprising the cellulose ester composition is an ophthalmic article, such as a spectacle lens or eye protection device. In embodiments, the ophthalmic article may be selected from an eyeglass frame, an eyeglass lens, a sunglass frame, a sunglass lens, safety glasses and/or lenses, goggles, or a face mask.

In embodiments, the article comprising the cellulose ester composition may be a household article or a consumer product in general that generates sound or is subjected to vibration, and may be selected from kitchen utensils, bar wine wares, outdoor furniture, interior furniture, furniture components, shelving dividers, slatted walls, toys, sporting goods, luggage, household appliances, small appliances, storage containers, office supplies, bathroom equipment or fixtures, tools, household electronics, commercial food service products, such as food trays, cups and storage cases, bottles, food processors, blenders and mixing bowls, utensils, water bottles, crispers, washing machine front panels, vacuum cleaner parts, or components thereof.

In embodiments, certain cellulose ester compositions are particularly useful for injection molded articles that are susceptible to damage from gate or weld induced impact (or stress), such as injection molded articles having relatively thin sections/regions near the gate or weld location of the mold, where increased stress concentrations occur at (or near) the gate or weld location of the molded article. In certain embodiments, a cellulose ester composition comprising a PBS polymer (or PAP), an impact modifier, and a monomeric plasticizer (as described herein) can provide improved gate and/or weld strength compared to a similar composition but without all three additives.

The invention can be further illustrated by the following examples of preferred embodiments thereof, but it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated.

Examples

Cellulose ester compositions are prepared by compounding the selected cellulose ester with a PBS polymer, an impact modifier, and/or a monomeric plasticizer. Unless otherwise specified, compounding of the cellulose ester composition was carried out on a Leistritz 18 mm (50L/D ratio) twin screw extruder at a throughput of 18 lbs/hr using a screw speed of 250 rpm and a barrel temperature of 220 ℃. The barrel temperature for compounding the CA and CAP141-20 based compositions was 230 ℃. The cellulose ester designations used in the following examples are indicated above in table 1.

The PBS polymers used in the examples are indicated in table 2 below.

TABLE 2 PBS polymers

PBS designation	Commercial PBS Material	MFR　190℃，2.16 kg	PSeq Mn Dalton	Elongation at Break (%)
					A	FD91	5	18744	210
B	FZ71	22	17203	170
					C	FD92PM	4	17948	380
D	TH803S	20	15744	300

FD91, FZ71, and FD92PM were obtained from PTT MCC Biochem. TH803S was obtained from Blue Ridge tunhe.

Examples include testing on injection molded plaques and splines. Unless otherwise specified, molding was completed on a Toyo injection molding machine with a barrel temperature of 240 ℃ (460 ° f) and a mold temperature of 70 ℃ (160 ° f). Unless otherwise specified, tg, haze, light transmission, clarity, melt viscosity, notched izod impact strength, and gate toughness were measured/determined as discussed below.

Glass transition temperature (Tg) was measured according to ASTM standard method D3418, where the sample was heated from-100 ℃ at a heating rate of 20 ℃/minute. DSC scans of the material blends can show multiple Tg transitions. If more than one Tg transition is measured during the scan, the glass transition of the matrix is defined as the highest Tg measured during the scan.

Haze and percent light transmission were measured according to ASTM D1003 on 102mm x 102mm x 3.2mm injection molded plaques. In embodiments, where a clarity grade is provided, the grade is determined by visual inspection, where a clear grade corresponds to a% haze of less than about 10%, a slightly hazy grade corresponds to a% haze of greater than about 10% or greater than about 15% and less than about 25%, and a hazy or hazy grade corresponds to a% haze of greater than about 25%.

Notched Izod impact strength testing was performed at 23 ℃ on 3.2mm thick molded bars after conditioning the bars at 23 ℃ and 50% RH for 48 hours after slitting according to ASTM method D256.

Gate and weld toughness tests were performed by first injection molding a square frame in a square picture frame mold with a cavity, each side of the square frame having a width of 0.5 inches (12.7 mm), a thickness of 0.125 inches (3.2 mm), and a length of 5 inches (12.7 cm). Unless otherwise specified, molding was completed on a Toyo injection molding machine with a barrel temperature of 240 ℃ (460 ° f), a mold temperature of 70 ℃ (160 ° f), an injection speed of 1.0 in/s (2.54 cm/s), and a pressure (injection/dwell) of 1600/1500 psi (10342/11032 kPa). The mold includes an approximately 1 mm diameter pin gate located at the face center (i.e., the center of the width and length dimensions) on one side of the frame and configured to introduce molten injection moldable material into the cavity such that the material flows through the frame cavity and meets and establishes a weld (where the material meets) approximately at the midline of the opposite side (from the gate). The configuration of the mold, along with the pin gates and welds, is depicted in fig. 1 (thickness dimensions not shown).

Two test bars were cut from each molded picture frame to provide bars having a width of 0.5 inch (12.7 mm), a thickness of 0.125 inch (3.2 mm) and a length of 5 inch (12.7 cm). Each material formulation tested was molded into a sufficient frame to make at least three bars of each type of test bar (including gate, weld and control bars). The three different test bars were a sprue test bar, a weld test bar and a control test bar (without the edge of the pin sprue or weld) as shown in fig. 1.

The gate and weld toughness was determined by measuring the impact strength at 23 ℃ on 3.2mm thick bars of each type according to ASTM method D3763 after conditioning the bars for 48 hours at 23 ℃ and 50% RH. The gate spline is impacted centrally on the opposite face of the gate, and the weld spline and the control spline are impacted on the respective faces (i.e., opposite the gate side of the frame). The test was repeated three times for each sample and the average impact value (of the three tests) was recorded.

Example 1 CAP with and without monomeric plasticizer

CAP numbers from Table 1 without any monomeric plasticizer (Ex.1-1) and with 10% DOA monomeric plasticizer (Ex.1-2) were each injection molded on a Toyo 110 Ton injection molding machine to 3.2mm thick by 12.8mm wide bars with a barrel temperature of 240 ℃ and a mold temperature of 70 ℃.

The clarity, melt viscosity, tg and izod impact strength of each sample were determined. The compositions and properties of the materials of examples 1-1 and 1-2 are listed in Table 3 below.

TABLE 3 clear CAP materials with and without monomeric plasticizers

Examples 1	CE weave Number (C)	Monomer plasticizer woven fabric Number (C)	Monomer plasticization Agent%	Clarification Degree of rotation	Tg (℃)	Bending die Measurement of	Notched Izod impact strength at 23 ℃, J/m
								1	482-20	0	clear and clear	147	2100	70.9
2	482-20	DOA	10	Clear and limpid	108	1200	312
								3	141-20	0	Clear and clear	174	3100	45.5

Table 3 shows the properties of CAP 482-20 blended with no monomeric plasticizer (Ex 1-1) and CAP 482-20 blended with monomeric plasticizer (Ex 1-2) and CAP141-20 without monomeric plasticizer (Ex. 1-3). Review of the table indicates that the plastic remains clear. CAP plastics without monomeric plasticizers have a relatively high glass transition temperature but a low impact resistance level. In contrast, plasticized CAP compounds have higher impact strength levels, but lower Tg's. It would be desirable to have a cellulose ester composition that has the advantages of both a high Tg and good impact resistance.

Example 2 CE and PBS blend

Different cellulose ester numbers (from table 1) were blended with different numbers and different amounts of PBS polymer and injection molded into 3.2mm thick by 12.8mm wide bars on a Toyo 110 Ton injection molding machine with a barrel temperature of 240 ℃ and a mold temperature of 70 ℃.

The clarity, flexural modulus, tg and notched Izod impact strength of each sample were determined. The composition and properties of the material of example 2 are listed in table 4 below.

TABLE 4 CE and PBS Polymer blends

Example 2	CE numbering	PBS numbering	% PBS	Clarity of reaction	Tg	Flexural modulus	Notched Izod impact Strength at 23 ℃, J/m
								1	482-20	FD92	10	Clear and clear	120	2102	140
2	482-20	803S	10	Clear and clear	120	2032	97
								3	482-20	803S	20	Clear and limpid	83	X	215.8
4	141-20	FD91	5	Clear and limpid	172	2983	116
								5	141-20	FD91	10	Clear and clear	168	3026	98
6	141-20	FD91	15	Clear and clear	162	2660	112
								7	141-20	FZ71	5	Clear and clear	161	2802	112
8	141-20	FZ71	10	Clear and clear	166	3191	110
								9	141-20	FZ71	15	Clear and clear	161	2445	114
10	141-20	803S	10	Clear and limpid	172	2835	116
								11	141-3	FD92	10	Clear and clear	172	2632	196
12	141-8	FD92	10	Clear and clear	172	2781	211
								13	141-20	FD92	10	Clear and clear	172	2983	212
14	141-20	803S	25	Clear and clear	149	X	X
								15	VM230	FD92	10	Clear and clear	182	2483	126
16	CAP202	803S	25	Clear and clear	163	1793	251

A review of Table 4 reveals that the CE/PBS compound has a higher Tg than examples 1-2 from Table 3. It is further shown that for CAP141-20, when PBS was added, a formulation with both a high Tg and increased toughness (i.e., impact strength greater than 96J/m) was produced, and that FD 92-numbered PBS produced the highest impact strength.

Example 3 CE, PBS Polymer and impact modifier blend

CAP 482-20 cellulose ester grades were blended with different grades of PBS polymer and impact modifier and injection molded into 3.2mm thick by 12.8mm wide bars on a Toyo 110 Ton injection molding machine with a barrel temperature of 240 ℃ and a mold temperature of 70 ℃.

The clarity, flexural modulus, and Izod impact strength of each sample were determined. The composition and properties of the material of example 3 are listed in table 5 below.

TABLE 5 blends of CE, PBS and impact modifier

Examples 3	PBS weave Number (C)	PBS weight The content of	Impact resistance improvement Sex agent	IM weight The content of	Clarification Degree of rotation	Impact of instrument Destruction of	Flexural modulus (MPa)	Notched Izod impact at 23 ℃ Strength, J/m
									1	803S	10%	M570	6%	Clear and clear	Toughness of	1828	251
2	FD92	10%	M570	6%	Clear and clear	Toughness of	1738	211
									3	FD92	10%	Blendex 338	10%	Is impermeable Ming dynasty	Toughness of	1666	204
4	FD92	10%	MBS	6%	Clear and limpid	Toughness of	1762	232

Kane Ace M570 acrylic resin and B564 MBS core-shell impact modifier were obtained from Kaneka. Blendex 338 ABS core-shell impact modifiers were obtained from Galata Chemicals.

Review of table 5 reveals that blending the acrylic core-shell impact modifier with PBS and CAP resulted in a toughness higher than a similar amount of either the acrylic core-shell impact modifier alone or PBS alone (example 2-2), in addition to good clarity. The selected materials were also injection molded into 3.2mm thick x 102mm x 102mm wide plaques on a Toyo 110 Ton injection molding machine with a barrel temperature of 240 ℃ and a mold temperature of 70 ℃ to perform instrumented impact testing according to ASTM D3763. Ductile failure mode is given in the case where the specimen is plastically deformed before fracture without a crack radiating more than 10 mm from the center of the impact point. In the case where the test area of the test specimen is broken into two or more pieces, has a sharp edge, and shows little plastic flow, a brittle failure mode is given. In Table 5, the toughness against impact fracture is ductile fracture.

Example 4 Gate toughness test

CAP number 1 from table 1 was blended with various amounts of M570 acrylic impact modifier, PBS and DOA monomer plasticizer. Unless otherwise specified, PBS is PBS number D (TH 803S). Each blend was injection molded into square picture frames (5 inches on a side as discussed above) on a Toyo 110 Ton injection molding machine with (unless otherwise specified) a barrel temperature of 240 ℃ (460 ° f), a mold temperature of 70 ℃ (160 ° f), an injection speed of 1.0 in/s (2.54 cm/s), and a pressure (injection/dwell) of 1600/1500 psi (10342/11032 kPa). Test bars having a width of 0.5 inch (12.7 mm), a thickness of 0.125 inch (3.2 mm) and a length of 5 inches (12.7 cm) were cut from the mold frame for instrumented impact testing according to ASTM D3763. The blend compositions and impact strength results are shown in table 6 below.

TABLE 6 sprue toughness of the blends

Examples 4-6, 4-7 and 4-12 to 4-14 were made with PBS number C (FD 92 PM). Examples 4-23 to 4-29 were molded with barrel temperatures of 241 ℃ (465 ° f) and mold temperatures of 79 ℃ (175 ° f), and examples 4-24 were molded at pressures (injection/dwell) of 1900/1800 psi (13100/12411 kPa). Examples 4-7, 4-17, 4-20 to 4-22 were molded with a mold temperature of 24 ℃ (75 ° f), examples 4-18 were molded with a mold temperature of 43 ℃ (110 ° f), and examples 4-19 were molded with a mold temperature of 63 ℃ (145 ° f).

Review of table 6 reveals that the blends comprising impact modifier, PBS and monomeric plasticizer have higher gate and weld impact values than the blends containing only one or two additives.

The above detailed description of the embodiments of the disclosure is intended to describe various aspects of the invention in sufficient detail to enable those skilled in the art to practice the invention. Other embodiments may be utilized and changes may be made without departing from the scope of the present invention. The foregoing detailed description is, therefore, not to be taken in a limiting sense. The scope of the invention is to be defined only by the claims, which follow as set forth in the normal patent application, and by the full range of equivalents to which such claims are entitled.

In this specification, reference to "one embodiment," "an embodiment," or "an embodiment" means that the feature or features referred to are included in at least one embodiment of the technology. Separate references to "one embodiment," "an embodiment," or "an embodiment" in this specification do not necessarily refer to the same embodiment and are not mutually exclusive, unless so stated and/or unless a person of ordinary skill in the art would be apparent from the specification. For example, features, steps, etc. described in one embodiment may be included in other embodiments, but are not necessarily included. Thus, the present technology may include various combinations and/or integrations of the embodiments described herein.

Claims

1. A cellulose ester composition comprising at least one cellulose ester, at least one Polymeric Aliphatic Polyester (PAP), at least one impact modifier, and at least one monomeric plasticizer,

wherein the at least one cellulose ester is Cellulose Acetate Propionate (CAP);

wherein the at least one PAP is poly (butylene succinate) (PBS) or a copolymer of poly (butylene succinate) and poly (butylene adipate) (PBSA);

wherein the monomeric plasticizer is present in an amount of 1 to 5 weight percent based on the total weight of the cellulose ester composition;

wherein the cellulose ester composition has a Tg of at least 110 ℃ and a notched Izod impact strength of at least 80J/m, measured according to ASTM method D256 at 23 ℃ using 3.2mm bars after conditioning the bars for 48 hours at 23 ℃ and 50% RH.

2. The cellulose ester composition of claim 1 wherein the cellulose ester composition further has a weld toughness and a gate toughness of at least 100J/m.

3. The cellulose ester composition according to claim 1, wherein said composition comprises 65-95 wt.% of said cellulose ester, 2-15 wt.% of said PAP, 2-10 wt.% of said impact modifier, and 1 to less than 5 wt.% of said monomeric plasticizer.

4. The cellulose ester composition according to claim 1, wherein said composition comprises 65-95% by weight of said cellulose ester, 2-10% by weight of said PAP, 2 to 10% by weight of said impact modifier, and 1 to less than 5% by weight of said monomeric plasticizer.

5. The cellulose ester composition according to claim 1, wherein said composition comprises 65-95% by weight of said cellulose ester, 2-10% by weight of said PAP, 4 to 8% by weight of said impact modifier, and 2 to 4% by weight of said monomeric plasticizer.

6. The cellulose ester composition according to claim 1 wherein said PAP is PBS or PBSA having an MFR (190 ℃,2.16 kg) of less than 25.

7. The cellulose ester composition according to claim 1, wherein said PAP is PBS or PBSA having an elongation at break of 250% or greater.

8. The cellulose ester composition according to claim 1 wherein said PAP is PBS or PBSA having a Polystyrene (PS) equivalent number average molecular weight (Mn) greater than 15,000.

9. The cellulose ester composition according to claim 1 wherein the cellulose ester is a Cellulose Acetate Propionate (CAP) containing from 10 to 40 wt% propionyl.

10. The cellulose ester composition of claim 1, wherein the cellulose ester composition has a notched izod impact strength of at least 200J/m measured according to ASTM method D256 at 23 ℃ using 3.2mm bars after conditioning the bars for 48 hours at 23 ℃ and 50% RH.

11. The cellulose ester composition according to claim 1, wherein the composition further comprises at least one additive selected from the group consisting of antioxidants, heat stabilizers, mold release agents, antistatic agents, whitening agents, minerals, UV stabilizers, lubricants, nucleating agents, glass fibers, carbon fibers, flame retardants, dyes, pigments, additional resins, and combinations thereof.

12. The cellulose ester composition according to claim 1, wherein the composition further comprises at least one additive selected from the group consisting of a colorant, a reinforcing filler, and combinations thereof.

13. The cellulose ester composition of claim 1 further comprising at least one polymer component as a blend wherein the polymer is selected from the group consisting of polyesters; a polyamide; polystyrene; other cellulose esters, cellulose ethers; a polystyrene copolymer; a polyolefin; a polyurethane; acrylonitrile butadiene styrene copolymers; poly (methyl methacrylate); an acrylic copolymer; poly (ether-imides); polyphenylene ether; polyvinyl chloride; polyphenylene sulfide; polyphenylene sulfide/sulfone; poly (ester-carbonates); a polycarbonate; polysulfones; polylactic acid; polybutylene succinate; polysulfone ethers; and poly (ether-ketones) of aromatic dihydroxy compounds; and combinations thereof.

14. The cellulose ester composition of claim 1 further comprising at least one polymer component as a blend wherein the polymer is a styrene acrylonitrile copolymer.

15. An article comprising the cellulose ester composition of any of claims 1 to 14.

16. The article of claim 15, wherein the article is selected from an injection molded article, an extrusion molded article, an injection blow molded article, an injection stretch blow molded article, an extrusion blow molded article, or a compression molded article.

17. The article of claim 15, wherein the article is an ophthalmic article.

18. The article of claim 17, wherein the ophthalmic article is a spectacle or sunglass frame.

19. A film or sheet comprising the cellulose ester composition according to any of claims 1 to 14.